The declaration came a day after Venezuela recalled its own ambassador to Spain following the European Union's adoption of sanctions against seven senior Venezuelan officials, including a freeze on their assets and a ban on traveling to the EU.
Venezuela "has decided to declare persona non grata the ambassador of the Kingdom of Spain to Venezuela... owing to its continuous aggressions and repeated acts of interference in the internal affairs of our country," the foreign ministry said in a statement.
Caracas accuses Spanish Prime Minister Mariano Rajoy of being one of the masterminds behind the sanctions, saying he was acting on instructions from the United States. Among the targeted officials was Diosdado Cabello, one of the most powerful figures in the Venezuela leadership.
Diplomats like Spanish ambassador Jesus Silva who are censured by being declared persona non grata are normally required to leave the country where they have been serving.
Spain and Venezuela have suffered from tense diplomatic ties since the late Socialist leader Hugo Chavez came to power in 1999. He was succeeded on his death in 2013 by Maduro.