Salmond was reacting to Rajoy who said Scotland would not automatically become an EU member state if it voted for independence from the United Kingdom.
The Scottish first minister said that the EU membership issue would be negotiated from “within” and not from the outside.
On November 27, Rajoy said if a “region” opted to leave a member state, it “would remain outside the European Union” and then require the agreement of all 28 EU members in order to join the bloc.
Scotland is to hold a referendum on its independence on September 18, 2014.
Meanwhile, Scottish opposition labor leader Johann Lamont accused Salmond of failing to understand the Spanish PM’s comments.
“Yesterday, the Spanish prime minister made it clear that, by leaving the UK, Scotland would also leave the EU and have to re-apply as a new member,” Lamont said.
The Spanish premier’s rightist government refuses to tolerate Catalonia’s independence from Spain and has threatened to block a referendum on self-rule, promised for 2014 by Catalonian regional President Artur Mas.
On November 26, the Scottish government’s 670-page comprehensive White Paper, described as a blueprint for its independence, said that Scotland would continue to be a member of the EU.