Sterling tucked home shortly before the hour, just when it looked like the game was getting away from England in all-too-familiar fashion.
The Manchester City forward finished from a pass by the excellent Kalvin Phillips to send 22,500 supporters at Wembley wild in the afternoon sunshine.
At that point, the fans were beginning to get restless, chanting for Jack Grealish as he warmed-up as the game appearing to be following a well-worn big tournament pattern for England.
England came flying out of the blocks, full of adrenaline and cheered on by the home crowd but they could not maintain the pressure and Croatia had asserted themselves by the mid-pointof the first half.
Phil Foden struck the base of the post after just six minutes and Phillips sent the tone for his own brilliant display with a volley which extended goalkeeper Dominiki Livakovic.
But in heat of nearly 28C, England soon wilted and you had to wonder if a repeat of their defeat in Moscow was on the cards.
Croatia were the savvier side either side of the interval, even if their only chance of note was an effort fired wide by Ivan Perisic on 27 minutes.
But Sterling struck at the perfect time, firing a shot through Livakovic after superb work from Phillips, who had glided past two players before releasing the ball.
Even at 1-0, memories of three years inevitably lingered but England restricted Croatia to just one more good opening with the last kick of the game, which was sent well over the bar.
The win should help to banish any remaining anxieties from 2018 and leaves England in a strong position to progress to the knockouts having won their hardest group game.