The protesters in Barcelona and Catalonia are angry at the crackdown on a separatist-led referendum on independence for the region, which is due to be held on October 1.
Many of the angry protesters have been waving Catalonia’s red and yellow flag while chanting “We will vote” and “Hello Democracy!”
The protests were sparked when the Spanish military police, the Guardia Civil, raided Catalan government offices on Wednesday and arrested dozens of officials.
Acting on a judge’s orders, police also raided newspaper offices in a bid to find campaign literature for the referendum.
The Madrid Government is thought to be facing one of Spain’s biggest political crises since the end of the Franco dictatorship four decades ago.
The Spanish government has claimed that Catalonia’s independence referendum is “illegal”.
In a television address, Catalan’s President Carles Puigdemont said: “The Spanish state has by all rights intervened in Catalonia’s government and has established emergency rule.
“We condemn and reject the anti-democratic and totalitarian actions of the Spanish state.”
Malena Palau, a 21-year-old student, said: “We want to vote because we have the right to decide, regardless of what we vote.”
A spokesman for the Catalan National Assembly said: “They made a big mistake; we wanted to vote and they declared war.”
Prime Minister Mariano Rajoy said the operations in Catalonia were the result of legal rulings.
He has called on Catalan leaders to cancel the vote saying: “Don’t go ahead, you don’t have any legitimacy to do it.
“Go back to the law and democracy. This referendum is a chimera.”
The Constitutional Court has suspended the vote after the central Government challenged its legality.
The Spanish Government announced on Friday it would take over the payment of essential services and and public workers’ salaries in Catalonia to prevent them from spending cash on the referendum.
Polls show that 40 per cent of Catalans support independence for the region.