According to local health services, four people have been wounded seriously, but remain in stable condition.
It was earlier reported that at least 844 civilians and 33 law enforcers were injured in the clashes that erupted in Catalonia during the referendum on Sunday, Sputnik reported.
Madrid officials sent the Spanish National Police Corps and Civil Guard who tried to prevent the region's residents from taking part in the vote.
Authorities in Catalonia are claiming that 90 percent of those who voted in the independence referendum are opting to break away from Madrid. Catalan President Charles Puigdemont said in a live televised speech on Sunday that Catalans had won the right to sovereignty.
Puigdemont has already called on the European Union not to ignore violations of human rights by the Spanish police during clashes with the supporters of referendum.