Barca went into the away match at the Balaidos stadium having won their opening four games in the top flight but their bid for a sixth title in eight years was checked in spectacular fashion by the modest Galician club.
Coached by Argentine Eduardo Berizzo, Celta handed out the biggest La Liga defeat to their opponents, excluding games against Real Madrid, in more than a decade and are joint top with Real and Villarreal on 13 points after five games.
Former Barca B team player Nolito was one of the architect's of his ex-club's downfall while Iago Aspas, back at Celta after a failed stint at Liverpool, struck twice.
Barca, who have 12 points, had more possession (56 percent to 44) and more shots on target (seven to five) but they paid dearly for missing chances and struggled to control a fired-up Celta.
Berizzo said his team had luck on their side but also praised his players for remaining true to their attacking style in a way that contrasted sharply with the defensive tactics Barca's opponents typically employ.
"The idea is to play our own way and try to be the protagonists irrespective of the opponent," Berizzo told a news conference.
"Football was the winner," added the 45-year-old, a former Celta player who coached in Argentina and Chile before taking over in Vigo in July 2014.
"I congratulate my players, they were perfect. The pressure the midfielders and forwards put on Barca stopped them from settling."
Barca coach Luis Enrique is credited with sowing the seeds of Celta's playing style when he was in charge there in 2013-14 and he had nothing but praise for their performance.
"What decided this game was how well Celta played," he said.
"When a team has played better than you there is nothing much you can say.
"I’d rather lose to a team that plays like Celta did today, without any tricks, purely winning through their football. I congratulate them and hope they can carry on playing like that."
(Reporting by Iain Rogers, editing by Tony Jimenez)
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