Thanks to a competitive 225/6 in 50 overs -- built largely around Campbelle's partnership with Chedean Nation (49 not out) -- West Indies put pressure on England, who later succumbed to Shamilia Connell's (3/38) pace to be all out for 218 in 47.4 overs.
West Indies had defeated tournament favourites New Zealand by just three runs in the opening match.
It was a collective performance from the West Indies, with Campbelle's half-century, combined with an even contribution from their bowlers and a spectacular catch from Deandra Dottin that delivered the win on Wednesday.
Campbelle's 69, along with important knocks from Nation (49 not out), Hayley Matthews (45) and Dottin (31) helped West Indies post a decent total and it proved to be enough as England continually lost wickets at vital moments in reply.
England's hopes looked bleak when they were reduced to 156/8 in the 35th over, but Sophie Ecclestone (33 not out) and Kate Cross (27) combined to put on 61 for the ninth-wicket to almost pull off an amazing late heist.
It came down to the last three overs and it looked like the duo were going to get the job done as England required just nine runs for victory and still had two wickets in hand. But Cross was run out at the non-striker's end when backing up and Anya Shrubsole was bowled by spinner Anisa Mohammed (2/24) three balls later to set off jubilant celebrations for the triumphant West Indies side.
The victory moves West Indies up to second on the table with two wins from as many games, while England languish winless in sixth and with plenty of work to do if they are to repeat their 2017 heroics.
It looked like the West Indies were on their way to a massive total when Matthews (45) and Dottin (31) put on 58 during the opening powerplay and then took the score to 81 without losing a wicket. But the introduction of Sophie Ecclestone (3/20) into the attack helped slow the scoring and the match almost turned on its head during an eventful 21st over as the West Indies lost three wickets in five deliveries.
Matthews was the first to go when she edged Ecclestone to Shrubsole and Dottin followed three balls later courtesy of some excellent fielding from the experienced Danni Wyatt.
The West Indies then lost skipper Stafanie Taylor first ball as Ecclestone gave England the ascendancy, only for Campbelle and Chedean Nation (49 not out) to fight back with an impressive 123-run stand for the fifth wicket.
Campbelle fell to Sciver (1/49) in the penultimate over when chasing quick runs, but the West Indies would have been happy with the score they put on the board after their mid-innings collapse.
Opener Tammy Beaumont (46) and middle order duo Sophia Dunkley (38) and Wyatt (33) all got starts for England, but none went on with it as the West Indies prevailed in a thrilling contest.
Brief scores: West Indies Women 225/6 in 50 overs (Deandra Dottin 31, Hayley Matthews 45, Shemaine Campbelle 66, Chedean Nation 49 ot out; Sophie Ecclestone 3/20) beat England Women 218 in in 47.4 overs (Tammy Beaumont 46, Danni Wyatt 33, Sophia Dunkley 38, Sophie Ecclestone 33 not out, Kate Cross 27; Shamilia Connell 3/38, Hayley Matthews 2/40, Anisa Mohammed 2/24) by 7 runs.