Spanish Prime Minister Mariano Rajoy said on Sunday that the rule of law had prevailed in Catalonia because an independence referendum in the region prohibited by the courts had been blocked.
"Today there has not been a self-determination referendum in Catalonia. The rule of law remains in force with all its strength," he said in a televised address.
Security forces "performed their duty" in Catalonia and respected a court order to prevent voting from taking place, he added in his first public comments on Sunday's banned referendum.
"It would have been easier for everyone to look the other way," the conservative prime minister said.
The referendum was a "real attack on the rule of law... to which the state reacted with firmness and serenity".
"We have fulfilled our obligation, we have acted according to the law and only according to the law," he added.
At least 92 people were injured clashes between police and protesters, two of them seriously, a spokeswoman for the Catalan government's health department said, out of a total of 761 people who went to hospitals and health centres.
Spain's interior ministry said 33 police officers needed medical treatment.
Police baton-charged and fired rubber bullets to disperse crowds protecting polling stations in Barcelona and other towns and cities in the Catalan region.
Videos posted on social media showed police dragging voters from polling stations by their hair, throwing people down stairs and attacking Catalan firefighters who were protecting polling stations.
Catalan president Carles Puigdemont said police had used "indiscriminate force" against people demonstrating "peacefully".
Police had closed 319 polling stations set up for the referendum, Catalan government spokesman Jordi Turull told a news conference.
The Catalan government had said on Friday this it would have some 2,300 polling stations across Catalonia but it was unclear how many actually opened.
Several leftist Spanish politicians have demanded Rajoy resign because of the police crackdown against the protesters.
But the prime minister blamed the unrest on the Catalan government.
"The responsibility for these acts solely and exclusively falls on those who promoted the rupture of legality and coexistence," he said.
He called the referendum a process that "only served to sow division, push citizens to confrontation and the streets to revolt."
"I will not close any door, I have never done it," the prime minister added, suggesting he would be willing to negotiate with Catalonia to try to satisfy the region's demands for greater autonomy.
"But it will always be within the framework of law and democracy," he said.
Polls show Catalans are divided on the question of independence but the vast majority back a legal referendum on the issue to settle the issue.