Ibai Gomez's brilliant solo strike secured a surprise 2-1 victory for promoted Deportivo Alaves as it overcame LaLiga champion Barcelona at Camp Nou.
In the first league encounter between the two sides since 2005-06, Mauricio Pellegrino's side were fantastic throughout, defending stoically before Deyverson's close-range strike put it ahead prior to half-time.
Barca finally made its domination pay after the interval, though, Jeremy Mathieu heading home the leveller after meeting Neymar's precise corner.
Mathieu squandered a golden opportunity moments later and, after having a goal ruled out for offside, Alaves restored its advantage when former Athletic Bilbao winger Gomez took advantage of slack Barca defending to drill home following a fantastic run.
With Real Madrid having made it three wins from three with victory over Osasuna earlier on Saturday, Luis Enrique's side piled on the pressure, but Alaves held firm to secure a famous victory and extend its unbeaten start to the season.
Barca was boosted by the return of Neymar after the Brazil forward led his nation to Olympic gold, though – most likely with an eye towards Tuesday's Champions League tie with Celtic – Luis Enrique elected to rest both Lionel Messi and Luis Suarez, instead handing a debut to Paco Alcacer.
But it was the visitor who was the first to have an attempt on goal, Jasper Cillessen, making his debut in the absence of Marc-Andre ter Stegen, equal to a well-struck drive from Gomez.
Fernando Pacheco was called into action for the first time on the half-hour mark, making an excellent save in order to tip Aleix Vidal's rasping effort onto the crossbar following a well-worked Barca free-kick.
In spite of Barca's possession, though, it was Alaves who took a shock lead when Deyverson latched onto a terrific cross from Kiko Femenia and tapped home past Cillessen.
Barca was shocked, but almost produced an immediate response when Neymar got onto the end of looping cross, only to head wide of a gaping goal, before Ivan Rakitic fired over from close-range on the stroke of half-time.
However, Barca wasted no time in restoring parity after the restart, the unmarked Mathieu rising highest to connect with Neymar's whipped corner and heading in past Pacheco.
Mathieu should have doubled his and Barca's tally moments later, but the France defender's effort was instead an early candidate for miss of the season, as he somehow thumped wide from six-yards out.
Alaves thought it had snatched a second when Edgar Mendes volleyed home, only for the strike to be correctly disallowed for offside, before Alcacer flashed an effort wide at the other end.
Luis Enrique decided to bring on the cavalry after the hour-mark, introducing both Messi and Andres Iniesta into the fray.
But they had little time on the pitch before Barca found itself behind once more, Gomez weaving his way into the area before despatching a low finish into the bottom corner.
And despite a late onslaught, including Messi's agonising injury-time miss, Barca could not muster a comeback as it slumped to a shock defeat, its first to Alaves since February 2000, and lost early ground on league-leader Madrid.
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