Bell, given the task of filling the opener's spot vacated by Kevin Pietersen following the South Africa-born batsman's limited overs international retirement, responded with 126.
But with England looking on course for a score in excess of 300, West Indies -- who won the toss -- managed to hold them to 288 for six, with off-spinner Marlon Samuels taking two wickets for 43 runs in nine overs.
West Indies have the batting to chase down that score, despite the absence of hard-hitting opener Chris Gayle, whose much anticipated international return after 15 months out following a spat with Caribbean cricket officials was delayed by a left shin injury.
This was only Bell's second hundred in his 109 one-day internationals, with the 30-year-old's 126 not out against India in 2007 also made here at the Rose Bowl.
Bell's previous best as a one-day opener was the 77 he posted against Australia in a 2007 World Cup match in Antigua.
This innings came just a day after Bell's participation in the first of a three-match series was put in doubt when he was struck on the chin batting in the indoor nets and had to have stitches inserted into the wound.
But, overcoming fears of a broken jaw, Bell and Warwickshire colleague Jonathan Trott (42) put on 108 for the second wicket after England had been nought for one following the third ball exit of captain Alastair Cook, caught behind off Ravi Rampaul.
There had been concerns England would struggle for quick runs at the top of the order in the absence of Pietersen, who finished his one-day career with back-to-back hundreds against Pakistan in Dubai in February.
But Bell, who was dropped from the Pakistan series, took 16 runs off the sixth over from seamer Andre Russell.
First ball, he advanced and drove Russell back over his head for a straight six -- Bell's first boundary of his innings -- and next ball a fierce square-cut flew over point for four.
Two balls later Bell pulled Russell for four and followed up by driving a wide half-volley through mid-off.
West Indies were convinced they had Bell, on 23, caught behind off Rampaul.
But umpire Richard Kettleborough was unmoved and West Indies, who'd already used their one allowed review of the innings on an unsuccessful lbw challenge against Trott, had to accept the umpire's verdict.
Trott was caught by wicket-keeper Denesh Ramdin off spinner Sunil Narine.
Eoin Morgan (21) helped Bell add 51 before playing on to Samuels.
Bell was out when he top-edged a slower ball from seamer Dwayne Bravo and Ramdin took his fourth catch of the innings to leave England 216 for five.
Craig Kieswetter (38 not out) and Stuart Broad (22 not out) revived the innings as 68 runs came off the final 10 overs.
