Catalonia "has won the right to become an independent state", the region's President has said as preliminary results showed 90% of voters were in favour of independence.
Carles Puigdemont has said he will keep his pledge to declare the region independent of the rest of Spain if the "Yes" vote wins Sunday's disputed referendum on secession.
He continued that a win of more than 50% would trigger a declaration of independence within 48 hours of the vote, regardless of the turnout.
The 54-year-old was speaking in a televised address just hours after voting stations closed in Catalonia and as Spain's Prime Minister condemned the referendum on independence and praised the police response.
In a separate televised speech Mariano Rajoy insisted no independence vote had taken place and said those organising the referendum had defied the rule of law.
He also praised police for their "firmness and serenity" following clashes in which Catalan health officials say 844 people and 33 police were injured.
Applause broke out at a polling station in Barcelona as ballots closed at 8pm local time. A few others remained open as people waited to vote.
A regional government spokesperson said preliminary results showed 90% of the 2.26 million Catalans who voted had backed independence.
Some 5.3 million people were registered to vote.
They continued that almost eight percent of voters rejected independence, while the remaining ballots were blank or void.
Barcelona's mayor Ada Colau said earlier that she wanted "an immediate end to police charges against the defenceless population".
Police baton-charged and fired rubber bullets to disperse crowds in Barcelona and other towns and cities.
Videos showed them beating people repeatedly as they try to confiscate ballots and ballot boxes.
Earlier Catalan government spokesman Jordi Turull blamed the violence directly on Mr Rajoy and interior minister Juan Ignacio Zoido.
He said actions by Spanish National Police and Civil Guard forces on Sunday were politically motivated and showed "a clear motivation to harm citizens".
Catalan international affairs director Raul Romeva said regional authorities would appeal to European bodies over Mr Rajoy's government's alleged violations of human rights.
The referendum was held by regional separatist leaders in defiance of Spain's Constitutional Court that had suspended the vote.
The Spanish government said the vote would be void and police sealed off many voting centres and used force to stop people from using their ballot.
Catalonia is one of the country's most affluent regions, contributing a fifth of Spain's economy, and separatist Catalans complain this is more than they get in return.
Foreign governments have been cautious in their response to the referendum.
Boris Johnson rejected opposition calls for the UK to intervene with the Spanish government over the police crackdown.
Labour leader Jeremy Corbyn had urged the government to intervene with Madrid over the police action.
The Foreign Secretary said: "The Catalonian referendum is a matter for the Spanish govt & people. Imp that Spanish constitution respected & the rule of law upheld.
"Spain is a close ally and a good friend, whose strength and unity matters to the UK."
Belgium prime minister Charles Michel said: "Violence can never be the answer! We condemn all forms of violence and reaffirm our call for political dialogue."
Scottish leader Nicola Sturgeon said on Twitter: "Regardless of views on independence, we should all condemn the scenes being witnessed and call on Spain to change course before someone is seriously hurt."
Following the referendum, one of Spain's two major labour unions has called for a general strike in Catalonia on Tuesday to protest against the police violence which has marred the vote.
The CCOO union has also called for protests Monday at noon in front of town halls across Catalonia.
Jordi Cuixart, leader of separatist group Omnium, also urged a general strike in Catalonia on Tuesday.