The ministry also stated that 12 policemen were injured during the referendum scuffle.
Earlier in the day, a number of polling stations opened across Catalonia. The Spanish government is considering the vote to be illegal and taking measures aimed at foiling the referendum.
According to media reports, police resorted to rubber bullets and tear gas to disperse the protesters, who attempted to prevent police from shutting down the polling stations. Barcelona Mayor Ada Colau said that over 460 people were injured in Catalonia during the region's independence referendum.