Gareth Southgate's crop are already being tipped by some to make history and go all the way in the tournament, but the visit of Croatia represents a stern test in front of 22,500 optimistic supporters.
Kieran Trippier's free-kick. Harry Kane's inexplicable miss. Mario Mandzukic's winner. The demons of the 2018 World Cup semi-finals still linger in the minds of these England players - several of whom stepped foot onto the field for that fateful night in Moscow.
Despite already gaining a measure of revenge over Croatia in the inaugural Nations League campaign, Southgate's men are under immense pressure to replicate that feat in the English capital as they endeavour to kick off the summer in the most perfect way imaginable.
A near-flawless qualification period meant that England's place in the Euro 2020 finals was never in doubt, and the Three Lions enter the weekend on the back of a six-game winning run across all competitions, but their two recent friendly victories were not all that inspiring.
Back-to-back clean sheets against Austria and Romania were welcomed with open arms, but only a Bukayo Saka winner could get England over the line against the former, while Marcus Rashford was the only man who could make the net ripple from 12 yards in a 1-0 triumph against Romania.
Traditionally, though, the opening 90 minutes of the European Championship has ended in calamity for England. While they are unbeaten in all their Wembley appearances at a major tournament, they have never won their first game of the Euros in nine attempts, and Sunday would be as good a time as ever to break that alarming duck.
The joy of destroying England's World Cup chances in 2018 was short-lived for Croatia as they fell victim to France's superiority in the final, and Zlatko Dalic has failed to inspire his side to keep up that magnificent hot streak over the past 12 months.
The Chequered Ones experienced a few wobbles in qualification for Euro 2020 but eventually made it through, and the less said about their most recent Nations League campaign the better, although they were up against stiff opposition in France, Portugal and Sweden.
Croatia were never expected to overcome Belgium in their most recent friendly fixture on June 6, where Romelu Lukaku's goal handed the world's top-ranked nation a 1-0 win, but their 1-1 draw with Armenia a few days beforehand certainly raised a few more eyebrows.
History does slightly favour the visitors ahead of their trip to Wembley, though, as while England just cannot seem to get over the line in their first game of the Euros, Croatia have come up trumps in four of their last five such matches as they seek to channel the spirits of the 2018 World Cup luminaries.
As mentioned, England overcame Croatia 2-1 in the 2018-19 Nations League four months after their World Cup exit - with a goalless stalemate sandwiched in between those two matches - and the last time these two countries locked horns in the Euros group stages saw the Three Lions prevail 4-2 in 2004.
England have been handed a timely defensive boost with the news that Harry Maguire is back in training ahead of the opener, but it would be a huge shock to see the Manchester United man risked from the off.
To combat the expected absence of Maguire, Southgate is understood to have trialled a three-man defence with Luke Shaw on the left, which could see Tyrone Mings drop out following an uninspiring performance against Romania.
Saka has also been struggling with a hip problem but was never expected to start in attack - which is where Southgate's biggest decisions lie - and the Three Lions boss has the unenviable task of choosing either one or two of Rashford, Jadon Sancho, Raheem Sterling, Mason Mount, Jack Grealish and Phil Foden to support talisman Harry Kane.
England possible starting lineup:
Pickford; Walker, Stones, Shaw; Trippier, Rice, Phillips, Chilwell; Mount, Grealish; Kane
Croatia possible starting lineup:
Livakovic; Vrsaljko, Vida, Caleta-Car, Barisic; Brozovic, Kovacic; Rebic, Modric, Perisic; Petkovic
We say: England 2-1 Croatia
While Southgate still has dilemmas in all areas of the pitch to solve, the Three Lions' youthful attacking talent can strike fear into the hearts of any European defence, and it is up to the likes of Grealish and Mount to justify their possible selections over the likes of Foden and Raheem Sterling.
Croatia's form over the past 12 months has been indifferent to say the least, but there is no writing them off. Both sides will of course be expected to finish in the top two come the close of play in Group D, but with the raucous home crowd making the difference that has been missing all season long, we are backing England's firepower to propel them to a first-ever opening day victory at the Euros.