Catalonia's emergency services say 761 people have been injured, some seriously, during the police crackdown on Sunday on a banned referendum on breaking away from Spain.
Police fired rubber bullets near at least one Barcelona polling station, and have clashed with protesters throughout Catalonia.
Police officers had stopped some people from voting, and seized ballot papers and boxes.
In the regional capital Barcelona, police used batons and fired rubber bullets during pro-referendum protests.
The Spanish Prime Minister Mariano Rajoy said Catalans had been fooled into taking part in an illegal vote.
Meanwhile, the regional government's spokesman, Jordi Turull, blamed the violence directly on Rajoy and Interior Minister Juan Ignacio Zoido.
Turull said that actions by Spanish National Police and Civil Guard forces on Sunday were politically motivated and showed "a clear motivation to harm citizens."
Catalan international affairs director, Raul Romeva, said that regional authorities would appeal to European authorities for Rajoy's governments' violations of human rights.
Spanish deputy prime minister, Soraya Saenz de Santamaria, said Spanish police have intervened with "firmness and proportionality" against the Catalan vote on secession.
De Santamaria said Spanish authorities acted in a professional and proportional way, and that they weren't going after voters, but referendum material.
She accused the Catalan government that is trying to hold the referendum of behaving with absolute irresponsibility.
She said, "There hasn't been a referendum or the semblance of one."