Spain's highest court previously declared the vote illegal, a decision that precipitated a government crackdown on voters and polling stations across Catalonia - a region in the northeast of Spain that borders France.
Authorities donned riot gear, confiscated ballot boxes, shot residents with rubber bullets and dragged voters from the polls.
The region, discontent of the "disproportionate support" it has received from the Spanish government considering its contribution to the national economy, attempted to stage an independence referendum in November 2014, only suspending the move following stern gestures from the government and the Constitutional Court.
The police closed hundreds of polling stations and seized the polls.
Lionel Messi of Barcelona celebrates scoring his side's third goal with Ousmane Dembele of Barcelona and Luis Suarez
Footage on social media showed riot officers kicking and using batons to beat men in firefighters' uniforms, amid growing violence in Barcelona and surrounding districts. A few remained open as people waited to vote.
Students wear Esteladas (Catalan separatist flag) during a demonstration in favor of the banned October 1 independence referendum in Barcelona.
A spokeswoman for the Catalan government had earlier said at least 92 people were hurt.
Voting stations are closing in Catalonia after a tumultuous referendum on independence from Spain.
The total number of the ballot papers preserved for the vote, not taken by Spain's authorities and counted by election committees was 2,262,424 pieces, Turull said.
Catalonia, a 32,000 square kilometre region of northeast Spain, is home to some 7.5 million people, with Barcelona as its regional capital.
Madrid is trying to intimidate Catalans into submission, but from what we've heard from citizens, the actions of the police have had the opposite effect. Despite their interference, almost three-quarters of the polling stations opened for the referendum on the independence of Catalonia and are working.