Defeat against Netherlands in their first match left La Roja needing to take at least a point from their South American opponents to remain in the competition, but goals from Eduardo Vargas and Charles Aranguiz secured a famous Chile win.
As a result, Chile have advanced into the last-16 stage of the competition alongside Netherlands.
Here, Sports Mole dissects the 90 minutes of action between the two Group B rivals.
On target: 9
On target: 4
Was the result fair?
In truth, it is difficult to argue that Spain deserved to take something from the match. A response was expected from the European and world champions following their 5-1 defeat to Netherlands last week, but it just never arrived. There was no real tempo to their work in the early stages, while Chile always looked capable of causing problems on the counter. At 1-0, Spain would always have had a chance, but the second Chilean goal was a serious blow to La Roja's chances. The statistics show that Spain had more attempts, but the majority of their efforts came from distance, with Chile goalkeeper Claudio Bravo untroubled for long spells. It was no hard-luck story for Spain this evening, with their performances over their two Group B matches simply not good enough to remain in the competition.
It was no surprise that head coach Vicente del Bosque made changes to his XI following the Netherlands match, with Xavi and Gerard Pique both left out in favour of Javi Martinez and Pedro. There was no real change to the shape of the side, however, with Diego Costa once more left too isolated in forward positions. It was also a surprise that Del Bosque selected both Xabi Alonso and Sergio Busquets in the middle of the park, especially with Koke in such brilliant form last season. As mentioned above, a serious response had been expected, but too often they were predictable in the final third, with Chile comfortable in dealing with the long balls into Costa or the snappy passes around the edge of the box. It has been the first tournament in a few years that Spain have lined up with an out-and-out striker, but it simply did not work. If Del Bosque had his time again, he might have gone with a 'false nine', with Cesc Fabregas the most likely to operate in that position. It is too drastic to say that Spain are no longer a force, but Del Bosque now needs to embrace the talented youth that he has at his disposal.
Seen as the dark horses for the tournament this summer, Chile followed up their 3-1 win over Australia in their first group match with another impressive performance and indeed three points this evening. Again it was a 3-5-2/5-3-2 formation for the South American outfit, with Alexis Sanchez operating close to Vargas, who led the line superbly. Following a brilliant first period, which saw Chile take a two-goal lead, it was questioned whether they could continue with the same intensity in the second 45 minutes.
Well, those fears were dispelled as the match advanced, with Spain unable to match the energy levels of the South American side. It was a match where the first goal was always going to be vital and the fact that Chile opened the scoring allowed them to absorb the pressure and counter, which continued to trouble a fairly laboured Spain midfield. Teams that have beaten Spain in the recent past have needed a certain amount of luck, but that was not the case this evening. In almost every single area, Chile were superior and indeed deserve their spot in the next round.
Sports Mole's man of the match
Arturo Vidal: At one point, it was seen as doubtful that Vidal would take part in the competition at all this summer following an injury. However, there were no signs of that this evening. The Juventus midfielder, who operated off the front two, was terrific, with his powerful running and incisive passing causing Spain all sorts of problems. As the match progressed, Vidal dropped deeper and also demonstrated his defensive qualities. It was a sensational all-round midfield display.
Unfortunately, it was another horror show from Iker Casillas this evening. The Real Madrid stopper was heavily criticised following his performance in Spain's group opener against Netherlands, but kept his spot in the XI. It was another disappointing night for the experienced goalkeeper, however, as he palmed a Sanchez free kick straight into the path of Aranguiz, who scored Chile's second of the night just before the interval.
It has been an eventful World Cup for referees this summer, but American Mark Geiger was not really troubled this evening. The 39-year-old was calm and composed as he went about his work and awarded just three yellow cards despite a number of late challenges. In truth, Geiger was not seen for long spells, which is always a good sign for a referee.
Spain: Spain face Australia on June 23 in a match that will decide who finishes third in the group.
Chile: Top spot will be up for grabs when Chile face Netherlands on June 23.