
Messi, who has scored 42 times at club level across all competitions this season, tucked a 77th-minute goal past Valencia goalkeeper Vincente Guaita to leave Real Madrid trailing by 10 points on the Spanish table.
Valencia, meanwhile, fall 20 points clear of the league leaders in third place after seeing their 11-game unbeaten run brought to an end.
Barca's win, their 23rd straight unbeaten result in La Liga, was Pep Guardiola's first at the Mestalla as manager.
Messi was uncharacteristically wasteful in front of goal, failing to convert three gilt-edged chances, each from within eight yards, and spraying another over the crossbar.
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