Villa scored the opening goal by slipping the ball under goalkeeper Wojciech Szczesny after latching on to Lionel Messi’s flick-on.
It was Messi’s 20th assist in 35 games this season to go along with 40 goals.
Barcelona goalkeeper Victor Valdes allowed huge space to the near post, enabling van Persie to tie the score with his eighth goal in his last 11 games.
Arshavin slotted in the winner in the 83rd off a cross from Samir Nasri on a rapid counterattack.
Arsenal need little reminding that Messi scored four times against them at the Nou Camp last season.
The sides meet again on March 8 and Pep Guardiola will still believe that his men can reach the last eight.
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