Spain demanded Sunday that Catalonia's separatist government call off an independence referendum, dismissing the vote as a "farce", as national police moved in to stop it.
"Continuing this farce makes no sense, this does not lead anywhere, they should stop it immediately," Deputy Prime Minister Soraya Saenz de Santamaria said.
The Catalan government has "behaved in an absolutely irresponsible manner, it tried to annul law and justice in Catalonia, and with it democracy," she added.
"I don't know in what world (Catalan president Carles) Puigdemont lives, but Spanish democracy does not work like this. We have been free from a dictatorship for a long time and of a man who told us his word in the law," Saenz de Santamaria added, in an apparent allusion to the Franco dictatorship.
Madrid has strongly criticised the Catalan government for pushing through laws that paved the way for the referendum in Catalonia's regional parliament with little debate or opportunity for opposition parties to adding amendments.
Madrid argues that the referendum is illegal as it goes against the Constitution. Catalonia's leaders retort they have a right to decide their future even if it not allowed by the Constitution.
At least 91 people were injured in Catalonia as police and protesters clashed over the referendum, including one with a serious eye injury, a spokeswoman for Catalonia's health department said.
Spain's interior ministry said at least 11 police officers were injured. It said protesters had thrown rocks at police.
"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," Madrid's representative in Catalonia Enric Millo told a news conference.
Police fired rubber bullets in Barcelona as they charged protesters who wanted to vote in the independence vote which was banned by Spain's central government and the courts, witnesses told AFP.
Millo, however, said the police response had been "proportionate".
He also said Catalonia's regional police force had sought help from national police to block voting from happening at 233 polling stations.
"This is a gesture than honours them," Millo said, just hours after he complained that Catalan regional police were not doing anything to prevent polling stations from opening.
Spain's Interior Minister Juan Ignacio Zoido also urged Catalan authorities "to stop this genuine madness", adding the computer system which Catalan authorities say they have set up to prevent people from voting twice in the referendum "does not work".
Officers from Spain's Guardia Civil police force visited the Catalan government's communications hub in Barcelona on Saturday, cutting its connections with polling stations and access to software that could have allowed an online vote.