The Catalan side won all seven of their opening fixtures but Flick's heavily rotated side came badly undone in Pamplona as Ante Budimir bagged a brace, scoring either side of Bryan Zaragoza's strike.
Pau Victor had given Barca a lifeline to pull them back into the game before Budimir netted his second from the penalty spot. Abel Bretones added a sensational fourth from the edge of the box, before substitute Lamine Yamal pulled one back with a fine effort of his own.
Victory would have matched Barcelona's best-ever start to a league campaign with eight consecutive wins, but they were not able to build on their four-point lead over second-placed Real Madrid.
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