Catalan officials say at least 337 people have been injured in clashes as police try to prevent voting in Catalonia's independence referendum.
The Spanish government has pledged to stop a poll that was declared illegal by the country's constitutional court.
Police officers are preventing people from voting, and seizing ballot papers and boxes at polling stations.
In the regional capital Barcelona, police used batons and fired rubber bullets during pro-referendum protests.
The latest injury toll was confirmed by a spokesman for the Catalan regional government, as well as the region's health department.
Separately, the Spanish interior ministry said 11 police officers had been hurt.
At a press conference, Spain's Deputy Prime Minister Soraya Saenz de Santamaria said police had "acted with professionalism and in a proportionate way".
Catalan leader Carles Puigdemont condemned the action of the national police and Guardia Civil, who were sent into Catalonia in large numbers to prevent the vote from taking place.
"The unjustified use of violence... by the Spanish state will not stop the will of the Catalan people," he told reporters.
But Spanish Interior Minister Juan Ignacio Zoido blamed Mr Puigdemont for what he termed the day's senseless events.
And the Guardia Civil tweeted (in Spanish) that it was "resisting harassment and provocation" while carrying out its duties "in defence of the law".
One voter, Júlia Graell, told the BBC that "police started to kick people, young and old".
She added: "Today, I have seen the worst actions that a government can do to the people of its own country."
The ballot papers contain just one question: "Do you want Catalonia to become an independent state in the form of a republic?" There are two boxes: Yes or No.
Ahead of the polls opening, the Catalan government said voters could print off their own ballot papers and use any polling station if their designated voting place was shut.
In Girona, riot police smashed their way into a polling station where Mr Puigdemont was due to vote.
Television footage showed them breaking the glass of the sports centre's entrance door and forcibly removing those attempting to vote.
However, Mr Puigdemont was still able to cast his ballot at another polling station.

That's their problem