A total of 337 people visited hospitals and health centres, a spokeswoman for the Catalan government's health department said. So far 91 have been confirmed as injured, one of them with a serious eye injury, she added.
Spain's interior ministry said 11 police officers had been injured in the clashes.
Hundreds of people had gathered before dawn at the polling stations set up in schools and other public buildings for the referendum which Spain's central government and the court have ruled is unconstitutional.
But police forced their way into many polling stations, especially in Barcelona, the Catalan capital, and Girona, the fiefdom of Catalan president Carles Puigdemont, a lifelong advocate of independence.
In some cases police fired rubber bullets or charged demonstrators who offered resistance, witnesses told AFP.
Videos posted on social media sites showed police pushing some demonstrators and even beating them with batons.
In one video protesters with their hands in the air can be seen surrounding a group of riot police chanting "Murderers! Murderers!".
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