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Rudi Garcia's side trailed to Joe Rodon's early opener at the Cardiff City Stadium. But De Bruyne levelled from the penalty spot and Thomas Meunier fired Belgium ahead before half-time.
De Bruyne converted another penalty in the closing stages before Nathan Broadhead got one back for the hosts. Leandro Trossard extinguished Wales' hopes of a dramatic finish as Belgium moved to the top of Group J.
Belgium are two points clear of second-placed North Macedonia, who were held to a 1-1 draw by Kazakhstan on Monday.
The Red Devils haven't lost a qualifier for the World Cup or European Championship in 46 games since Gareth Bale sealed Wales' shock victory against them in 2015.
Wales sit in third place after squandering a chance to move a step closer to next year's tournament in the United States, Canada and Mexico.
