"Spanish democracy faces its greatest challenge," headlined top-selling El Pais daily just hours before police moved in en masse to seal off polling stations and seize ballot boxes, sparking scuffles as they sought to block the vote.
At least 38 people were injured in the clashes, along with another 11 policemen, officials said.
More than 5.3 million people have been called upon to have their say on independence from Spain in the wealthy northeastern region which has its own distinct language and culture.
But it has been ruled unconstitutional by the the central government in Madrid and the courts, with judicial officials ordering police to seize ballot papers, detain key organisers and shut down websites promoting the vote.
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Thousands of Spanish police fanned out across the region today, forcing their way into polling stations.
In central Barcelona, riot police charged at demonstrators who were sitting on the ground blocking their way after they raided a polling station at a school, witnesses said.
They also said police had fired rubber bullets, with one man showing AFP a leg injury he suffered.
"The unjustified use of violence, which is both irrational and irresponsible, by the Spanish state will not stop the will of the Catalan people," Catalan leader Carles Puigdemont said.
The police, he said, had used "batons, rubber bullets and indiscriminate force" against people demonstrating "peacefully".
"The head of a cowardly government has flooded our city with police," Barcelona Mayor Ada Colau wrote on Twitter, adding: "Barcelona city of peace, we are not afraid" -- a slogan coined after August's jihadist rampage that killed 16 people.
Riot police also stormed a polling station near Girona, smashing the glass doors of the sports centre where Puigdemont was due to vote, then cutting a chain to force their way in.
The drama unfolded after a night of tension in which thousands of people, both nervous and excited, had gathered outside polling stations before dawn, joining those who had spent the night camping inside to ensure they would be open on the day.
Under a sea of umbrellas outside a school in Barcelona, a mixed crowd of people gathered to vote, among them elderly people in wheelchairs, families with buggies and parents clutching toddlers by the hand. With no police in sight, they were able to cast their ballots, prompting scenes of jubilation.
"That's the great hope, to be able to vote freely like this despite the problems we've faced, I'm very happy. I can die peacefully," added Jose Mas Ribas, 79.
Elsewhere in Barcelona, rows of police vans lined the streets, their blue lights flashing as officers in riot gear, some carrying heavy bolt cutters, walked past crowds massed outside another polling station.
"Votarem, votarem!" -- Catalan for "We will vote!" -- they chanted, many with their hands in the air.
Although Catalans are divided over independence, most want to vote on the matter in legal, binding plebiscite.
"Puigdemont and his team are solely responsible for all that has happened today and for all that can happen if they do not put an end to this farce," Enric Millo told a news conference.
"The sole objective of today's operation has been to ensure that this illegal referendum does not take place and the Spanish and Catalan people can continue to live in peace and liberty as they have these past 40 years."
Pro-separatist lawmakers in Catalonia have pushed for an independence referendum since September 2015 when they won a narrow majority of 72 seats in the region's parliament.
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