Police have smashed their way into a polling station in Catalonia in a bid to shut down a banned independence referendum and there were reports of officers firing rubber bullets in the regional capital Barcelona.
Catalan emergency services said 38 people were hurt, mostly with minor injuries, as a result of police action on Sunday.
Police burst into the polling station in a town in Girona province minutes before Catalan leader Carles Puigdemont was due to vote there. They smashed glass panels to force open the door as voters, fists in the air, sang the Catalan anthem.
Police also fired rubber bullets in central Barcelona, El Periodico newspaper reported, at the intersection of two streets as violence erupted during the vote which has thrown Spain into its worst constitutional crisis for decades.
Officers with riot shields jostled with hundreds of voters outside one station at a school in Barcelona as the crowd chanted "We are people of peace!" Armoured vans and an ambulance were parked nearby.
The referendum has been declared illegal by Spain's central government in Madrid, which says the constitution states the country is indivisible and has drafted in thousands of police from around Spain into Catalonia to prevent the vote.
The Catalan regional government had scheduled voting to open at 1900 AEDT at around 2300 stations, but Madrid said it had shut more than half of them.
Voting started at some sites in the region of 7.5 million people, which has its own language and culture and is an industrial hub with an economy larger than that of Portugal.
Leader Puigdemont changed plans and voted at a different station after the police action, the regional government said.
People had occupied some stations with the aim of preventing police from locking them down. Organisers smuggled in ballot boxes before dawn and urged voters to use passive resistance against police.
In a school used as a polling station in Barcelona, police in riot gear carried out ballot boxes while would-be voters chanted "out with the occupying forces!" and "we will vote!".
The Catalan government said voters could print out ballot papers at home and lodge them at any polling station not closed down by police.
"I have got up early because my country needs me," said Eulalia Espinal, 65, a pensioner who started queuing with around 100 others outside one polling station, a Barcelona school, in rain at about 5am
"We don't know what's going to happen but we have to be here."
Around 40 per cent of Catalans support independence, polls show, although a majority want to hold a referendum on the issue.
The ballot will have no legal status as it has been blocked by Spain's Constitutional Court and Madrid has the ultimate power under its 1978 charter to suspend the regional government's authority to rule if it declares independence.
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