However, a swift injury-time counterattack triggered by Lorenzo Insigne allowed Matteo Darmian to play a low cross into the path of Graziano Pelle, who volleyed home to set off wild celebrations in the Azzurri camp.
Here is how Sports Mole covered the game in Paris.
4.03pmToday's clash of the titans at the Stade de France is the 35th encounter between the Azzurri and La Roja, with a perfectly poised record of 10 wins for each side and 14 draws so far.
4.06pmRecent history seems to favour the defending European champions though - Italy have not beaten Spain in a major tournament since the 1994 World Cup, and were knocked out by them in Euro 2008 and at the 2012 final - that famous 4-0 victory in Kiev.
4.10pmSo Italy, who switched their starting XI round in their 1-0 defeat against the Republic of Ireland, have reverted to type and make seven changes back to their first team - the only notable tweak is that Mattia de Sciglio comes in for the injured Antonio Candreva at right wing-back.
4.12pmSpain manager Vicente del Bosque, meanwhile, resists the temptation to make any changes despite their last-gasp defeat against Croatia that saw them slip to second in their group - the fourth game in a row that he keeps the faith.
4.14pmWhichever team wins this game cannot exactly breathe a sigh of relief - up next for the victor is a meeting with none other than world champions Germany in the quarter-finals.
4.16pmAnd after that, it's a semi-final tie with either England, France or Iceland - who would very quickly become the story of the tournament should they overcome the Three Lions and Les Bleus. Great news for the neutral, who gets to witness some bumper match-ups, not so much for the fans of those teams.
4.19pmYou have to feel for the Italians, don't you? One of the first teams to clinch qualification from the group stages with wins over Belgium and Sweden, and by virtue of Croatia's victory over Spain, the Azzurri end up drawing arguably their bogey team, which just so happens to be one of the strongest nations in the world.
4.22pmItaly defender Giorgio Chiellini also recognises the danger that Spain pose. Ahead of today's match, he said: "The beginning of their golden period coincided with their win over us in 2008."
4.24pmHowever, he suggested that La Roja's 4-0 thrashing over his nation in the Euro 2012 final was an anomaly. He continued: "It was only in Kiev that we weren't able to give them a game, we hadn't been able to recover from our game against Germany."
4.26pm"In all the others we saw more balanced games decided by incidents. That's how the game will be on Monday... details can make all the difference."
4.28pmToday's fixture in Paris will be the fourth time the sides have met in the last three European Championships, and the sixth overall - making it the most played fixture in the tournament.
4.30pmFor the more eagle-eyed football aficionados, they also faced off just a year after the Euro 2012 final at the Confederations Cup - it ended as a 0-0 draw after 120 minutes, followed by a penalty shootout won 7-6 by Spain. So it's most likely going to be on a knife-edge.
4.33pmThere will be an interesting clash today between Juventus striker Alvaro Morata, lining up in the red of Spain, trying to get past his club teammates Andrea Barzagli, Leonardo Bonucci and Giorgio Chiellini - arguably one of the most feared defensive combinations in world football today.
4.35pmMorata even warned of what he can expect on the Stade de France pitch in a recent interview, joking: "They've told me to wear a helmet to play against them."
4.38pmBarzagli also echoed these sentiments about putting club camaraderie to one side: "There are no friends on the pitch. I struggle even to say hello to them before kick-off, as it's an issue of concentration. Morata is one of many dangers in the Spain side. They have a lot of quality and we must be wary of everyone."
4.42pmAt this stage it's also worth looking at what players are on a yellow card and could be suspended for the following game should they get through:
4.45pmNow let's look at some more statistics surrounding this titan of a fixture, and the two teams involved.
4.47pmItaly have failed to score in three of their last four knock-out games at the Euros - with the exception their 2-1 win against Germany in the semi-finals in 2012.
4.49pmThe Azzurri have also never scored more than two goals per match in their 36 games at the European Championship, so a bet on Italy doing a Netherlands against Spain as per the 2014 World Cup is probably not a good idea.
4.52pmMeanwhile, the Spanish have lost three of their last six games at the World Cup and European Championship - as many defeats as in their previous 31 major tournament games. Will today be another nail in the Tiki Taka coffin for them or a triumphant return to form?
1 minKICK OFF: Here we go! Italy vs. Spain is now underway!
1 minDe Sciglio tries to carve out an opportunity by whipping a cross into the box, but De Gea comes off his line to gather the ball.
2 minMore from Italy as De Rossi's huge crossfield pass finds Florenzi, whose cross is soon cleared by Ramos. All of a sudden it's started raining very heavily in Paris.
5 minSpain put together their first decent passing move, but Nolito slips over on the left wing. Moments earlier Eder fell because of the slippery pitch too. Fertile ground for mistakes to happen.
7 minItaly get the ball to Eder in the penalty area - he makes a decent connection with his shot but Ramos is there to charge the effort down.
8 minSAVE! What a save from De Gea! Pelle was on hand to latch on to a free kick and thump a header towards the bottom corner, but the goalkeeper shows his reflexes and palms the ball out for a corner!
11 minOFF THE POST! And De Gea does it again! Pelle heads a Florenzi ball across the face of goal, Giaccherini improvises an overhead kick, and the Man Utd stopper gets down to his left and pushes the ball onto the post. The referee blows his whistle moments later for infringement.
14 minNow it's Spain's turn to head forward as Silva marauds down the right flank, cuts inside onto his left foot and attempts to pick out the run of Alba at the far post, but the wet surface and the weight on the ball means it's beyond the latter's reach.
16 minThat save from De Gea really was something special. He's going to have a big say in this game.
20 minSpain, who have been second best thus far in the game, show a bit more attacking intent as Fabregas collects a ball in the D and strikes a shot towards goal that is well blocked by De Sciglio. Probably La Roja's best passage of play just there.
22 minMorata strikes the ball against Chiellini and wins Spain a corner on the far right-hand side.
23 minThe corner is played short to Iniesta and curled to the far post, where Ramos goes down at the hands of a challenge from Chiellini. Nothing given - looked a bit theatrical.
24 minBOOKING:Mattia De Sciglio is the first man to go in the book in this game due to a shirt pull. He was one of the few Italy players not on a yellow ahead of kick-off.
25 minCHANCE! Parolo finds himself some space in the box, connects with De Sciglio's inswinging cross and plants a header goalwards, but the ball goes wide of the right post!
26 minMorata holds his face after finding himself on the receiving end of a pretty firm elbow from Parolo - nothing given though.
28 minAlba's cross is turned behind for a corner, which is played to Iniesta, but the midfielder's 25-yard attempt is easily saved by Buffon.
29 minSpain are under siege again as De Sciglio's low cross from the left is dangerously shanked wide of his own goal by Ramos on the six-yard line - two corners are taken in quick succession, but the outcome is a free kick to the European champions.
32 minRamos brings down Pelle and concedes a free kick in a promising position for Italy. Eder takes from 25 yards...
35 minThe Azzurri edge themselves into a deserved lead as Chiellini was in the right place at the right time - De Gea keeps out Eder's free kick, but the Juve defender follows up on the rebound! First blood to Italy!
36 minSpain set about trying to get themselves back into contention, but Italy appear keen to avenge their Euro 2012 defeat - Pelle slides through Iniesta, giving Del Bosque's side a foul 35 yards from goal, but nothing comes of it.
38 minA rare mix-up among the Italian back line leads to a Spain corner. Nolito takes it but it's punched to safety by the evergreen Buffon.
40 minBOOKING: The first Roja player finds his way into the ref's book as Nolito launches into a late tackle on De Rossi.
42 minNolito gets to the byline and pulls a cross back to the edge of the penalty area for Pique, but he can't get to it as Italy clear their lines.
45 minCHANCE! De Gea is keeping Spain from finding themselves on the receiving end of a thrashing as Giaccherini jinks his way through multiple challenges and fires the ball from the edge of the box, but the Man Utd man is on top form once again to get it behind for a corner.
5.48pmWell, this is not something we expected, is it? Spain have the better team on paper, and all the signs pointed towards a very close game, but Italy have been rampant here at the Stade de France.
5.49pmLa Roja, who were THE international team between 2008 and 2012, now find themselves with serious work to do as The Azzurri have been tactically perfect to end the first half in the lead.
5.52pmGiorgio Chiellini's rebound strike following Eder's free kick puts Antonio Conte's charges in the lead, but David de Gea has pulled off three world-class saves to ensure his side are just one goal down at the break - Italy would be out of sight were it not for him.
5.55pmVicente del Bosque will need to reshuffle his formation and possibly make a change or two to help Spain back into the game, because as things stand, he is being outfoxed by the soon-to-be Chelsea boss and his side will be experiencing a second consecutive early tournament exit.
5.57pmThat said, Italy's goal appears to be more a case of bad defending on Spain's part - Pique and Iniesta weren't even looking at the ball, De Gea wasn't quite ready, and there was a big gap in the wall in line with the centre of the goal.
6.00pmSUBSTITUTION: As predicted, Spain make a change - Nolito comes off, Aduriz comes on. An attacking change by the looks of things.
46 minKICKOFF: Second half is underway. Will Spain pull something out of the hat or are Italy going to book a quarter-final date against Germany?
46 minAnd Italy are straight out of the starting blocks at full tilt once again - Florenzi breaks into the box on the right and plays a dangerous low cross that Pique touches behind for a corner, and from the set piece, Ramos is forced to clear on the six-yard line.
50 minCHANCE! Bonucci gives a free kick away, which is swung in by Silva and headed behind by De Rossi - the ensuing corner results in a free header for Morata, but it's straight at Buffon from six yards out!
52 minThis is a bit better by Spain as they begin to apply pressure on Italy - Pique tries to force a shot but it's charged down by the Azzurri defence, before Fabregas skies an effort way over the bar.
53 minSUBSTITUTION: Daniele De Rossi's involvement today is over - the Roma veteran is replaced by Thiago Motta.
54 minBOOKING: Pelle goes into the ref's book for an aerial challenge on Fabregas - the midfielder went down holding his face, but that looked a bit theatrical as well, in all honesty.
55 minCHANCE! And De Gea pulls another great save out of his hat once again! Eder latches on to a precise pass and, one-on-one with the keeper, lets rip with a precise shot towards the post that De Gea manages to keep out Peter Schmeichel-style!
57 minAduriz goes down with a nosebleed, so there's a short break while he gets treatment.
59 minIt's getting quite tempered here as Pique takes out Eder with a shoulder barge, but the referee allows play to go on.
61 minMorata whips in a dangerous looking cross but it's easily dealt with by Buffon, who makes a comfortable catch. If Spain get back into this game and go on to win, much credit needs to go to De Gea - this could well have been a Netherlands-style drubbing were it not for him.
62 minWith regards to De Rossi, it looks like he was subbed off because of injury - his eye was being tended to by medical staff following his exit from the game.
62 minCHANCE! Yet another foray by Italy as Eder rides a tackle and gets the ball to De Sciglio, whose subsequent shot-cum-cross slips out of De Gea's grasp but falls to a Spanish defender, who clears the danger.
64 minIniesta attempts to slip a ball into the path of Aduriz, but Italy keep things tight at the back with Bonucci getting rid of the danger.
66 minNow Juanfran tries to get the better of De Sciglio but the AC Milan man stands his ground to make a superbly timed tackle. Italy's defence is superbly well-drilled.
69 minCHANCE! De Sciglio switches off for a nanosecond - and that's all it takes for Spain to breach the Italian defence, with Aduriz getting into a good position and flashing a snapshot towards goal, but it ends wide.
70 minSUBSTITUTION: Lucas Vazquez replaces Alvaro Morata for Spain.
71 minCHANCE! Spain are knocking on the door, with Fabregas's outswinging corner kick falling into the path of Ramos, who nods the ball just wide.
73 minAt this stage, Italy have no suspensions for a potential quarter-final, though eight of their players are on a yellow – six from before the game, two during it.
74 minCHANCE! Aduriz takes the ball down on his chest on the edge of the Italy penalty box and gets the ball over to Vazquez, who fires against the post - but the move is thwarted for offside.
76 minCHANCE! Spain's knocking is turning into shoulder-barging - Iniesta lets rip with an effort directed towards the underside of the crossbar, which Buffon knocks away for a corner, and moments later Pique attempts a long-range shot which the Juve stopper once again keeps out!
78 minWe're heading into the last 10 minutes of the game plus stoppage time - Spain are turning the screw on Italy, who may come to rue their missed plethora of chances.
80 minSUBSTITUTIONS: Changes for both sides as Aduriz, who is hobbling, is replaced by Pedro, while Italy make their second change with Lorenzo Insigne replacing Eder.
81 minSpain have had 75 percent possession in the last 15 minutes - Italy appear to be missing De Rossi's influence in midfield.
85 minInsigne tries his luck with a long-range shot directed towards the middle of the goal, but De Gea is alert and on hand to make a comfortable save.
86 minSpain have scored 16 goals in the last 10 minutes of European Championship games, more than any other side in the competition's history. Could this stat apply tonight too?
87 minCHANCE! Spain come close once again as Iniesta gets the ball to Silva, who plays in a low cross that skims off the foot of Barzagli - but is also too heavy for the stretching Pedro a few yards from goal.
89 minBOOKING: Motta is shown a yellow card for a clash with Vazquez - he will miss the quarter-final should Italy see the game out.
89 minBOOKING: Busquets also gets his name in the referee's book for complaining.
90+2 minIt really looked like Spain could have nicked a late goal, but it's all over now as Italy get a second strike to send the champions tumbling out! Insigne sends a crossfield pass to Darmian on the right - the Man Utd man then whips a low cross which is deflected into the path of Pelle, who subsequently volleys home from a few yards out.
6.53pmSpain are out of the tournament as Italy put in a superb performance, ride out the ensuing storm and then kill off the Euro holders with a late goal!
6.55pmGiorgio Chiellini opened the scoring for the Azzurri with a first-half goal, and despite an onslaught by Vicente del Bosque's charges in the second half, Graziano Pelle put the final nail in the Tiki Taka coffin - Italy's bogey team is out of the way, and the Azzurri are through to the quarter-finals, where they will meet world champions Germany!
6.55pmWell folks, it's been a pleasure, but it's time for me to wrap this up - but don't go anywhere because now it's time for England to take on Iceland! Thank you for following and bye-bye!