The powerful left-hander smashed 11 sixes and five fours as the Windies successfully chased down England’s score of 182 for six at the Wankhede Stadium.
Destructive opener Gayle was largely off-strike in the opening stages of the Super 10 Group One clash but lit up the tournament when the opportunity came his way.
He hit two consecutive sixes off spinner Adil Rashid in the ninth over as the West Indies sat at 85 for two at the half-way stage of their innings.
Gayle, 36, then repeated the feat against Ben Stokes in the 11th as he single-handedly took control of the Windies’ assault on England’s total.
Opener Johnson Charles had gone for nought in the first over while Marlon Samuels had made a speedy 37 before being caught deep by David Willey off Rashid.
Denesh Ramdin went for 12 while Dwayne Bravo could manage only two, but Gayle remained destructive as partners fell around him.
The Jamaican, who was accused of sexism after he asked an Australian TV presenter for a date live on air in January during the Big Bash League, hit one monstrous six after another.
He clinched his century in the 18th over with a quick single as he finished on 100 not out from 48 balls.
Andre Russell hit the winning run as the West Indies beat the target set them in 18.1 overs.
England’s stand came after West Indies captain Darren Sammy won the toss and elected to field.
Joe Root top-scored for England with a tidy 48, including two exquisite sixes, off 36 balls at the western Indian city’s Wankhede Stadium.
England skipper Eoin Morgan had promised his charges would bat aggressively but they looked nervy in the opening stages and took their time getting runs on the board.
They posted just five runs in the opening two overs before openers Jason Roy and Alex Hales began to get into their groove as England reached 36-0 after four overs.
But right-handed batsman Roy was expertly caught at midwicket in the fifth over for 15 by a diving Samuel Badree off Russell, sporting an orange mohawk hairstyle.
Hales and number three Root then struck up a healthy partnership as England quickened their run-rate, reaching 81 for one after 10 overs.
The partnership was at 55 runs when six foot seven inches left-arm spinner Sulieman Benn bowled Hales in the 12th over with England’s opener having made 28.
Root then went when he miss-hit a Russell delivery straight to Jerome Taylor, who pouched the ball with ease at mid-off.
Jos Buttler made 30, including three sixes, before being caught by Carlos Brathwaite in the deep, while Morgan scored 27 not out.