The 38-year-old forward, who will retire at the end of the season, had only been on the pitch for a minute when he met Ander Capa’s cross with an acrobatic volley to bag a sensational 89th-minute winner at San Mames.
Defending champions Barca were without star man Lionel Messi, who is recovering from a calf injury, and were dealt a further blow when Luis Suarez was forced off with an apparent calf issue of his own late in the first half.
Suarez had squandered Barca’s best chance of the match, hitting the left-hand post after receiving a misplaced backpass in the penalty area, but it was Bilbao who looked most likely to make the breakthrough for much of the opening period, with Inaki Williams looking especially dangerous.
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