Mr González has been in hiding, and a warrant issued for his arrest after the opposition disputed July's presidential election result - in which the government-controlled National Electoral Council (CNE) declared Nicolás Maduro the winner.
Venezuela's Vice-President Delcy Rodríguez said in a post on social media that after "voluntarily" seeking refuge at the Spanish embassy in Caracas some days ago, Mr Gonzalez asked the Spanish government for political asylum.
She added that Caracas had agreed to his safe passage and that he had left.
Spain's Minister of Foreign Affairs José Manuel Albares said Mr González had departed the country at his own request, and on a Spanish Air Force plane.
BBC