Manchester City winger Raheem Sterling scored the only goal of the match in the 57th minute as Gareth Southgate’s men opened Group D with a victory, which Scotland will hope to emulate in their first match against the Czech Republic at Hampden on Monday.
Three years on from their heartbreaking extra-time loss to the Croatians in the World Cup semi-final, England exacted some sort of revenge by triumphing in front of a pulsating, partially filled Wembley.
There was a surprise in the Zlatko Dalić’s starting line-up with Rangers defender Borna Barisic left out of the squad altogether and replaced by 19-year-old Josko Gvardiol of Dinamo Zagreb.
A smattering of jeers when players took the knee before kick-off made way for a start as lively as the socially distanced crowd at the first major men's international tournament match on home soil since Euro 96.
Phil Foden's new bleach-blond look has been likened to Paul Gascoigne's back then and the 21-year-old came close to producing a moment of magic the England great would have been proud of when hitting a post.
England shone during that encouraging opening 20 minutes, only for Croatia to settle and take the sting out of a sharp attack that continued to underwhelm early in second half.
The Three Lions had never previously won their opening game at a European Championship and, just as fans began to worry that run might continue, a moment of incision cut the visitors' backline open.
The impressive Kalvin Phillips cut inside and smartly put through Sterling to smash home his first tournament goal as fans celebrated a Three Lions strike at Wembley for the first time since November 2019.
It proved the winner at the end of a week to remember for the 26-year-old, who was made an MBE for his work for services to racial equality in sport in the 2021 Queen's Birthday Honours.
Sterling continued that fight by taking the knee before kick-off alongside his team-mates, with some ignoring pleas to respect players by booing the gesture before applause and cheers drowned the minority out.