Celta’s towering centre-forward proved the thorn in Barcelona’s side once again after the break and had completed his hat-trick within 17 minutes of the restart.
Two expert finishes exposed a disorganised defensive line, with Frenkie de Jong culpable for gifting the visitors their second of the afternoon.
But Barcelona refused to accept defeat and within six minutes had produced a stunning comeback to level proceedings.
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Quick-fire strikes from substitute Dani Olmo and the effervescent Raphinha brought the hosts back into the action, setting up a finely-poised finale.
The hosts pushed frantically for a winning goal and eventually grabbed it as VAR awarded a penalty for Yoel Lago’s challenge on Olmo in stoppage-time, with Raphinha coolly converting from the spot to secure a hugely important victory for Hansi Flick’s side.