Prime Minister Mariano Rajoy ordered the deputy prime minister Soraya Saenz de Santamaria to take control of Catalonia in an unprecedented effort to quash its attempts at secession.
Overnight there were fights in Barcelona as both sides of the debate took to the streets and grappled with police and more protests have been planned in Madrid today.
Mr Rajoy has issued a decree confirming the sacking of Josep Lluis Trapero, head of the regional police force, the Mossos d’Esquadra.
At the University of Barcelona, intense rows erupted across lecture halls between either side of the debate.
Spain is adamant it will impose direct control, but the Catalan parliament is certain they will declare independence.
At least two men were injured in the violence but this figure is expected to increase.
More violence could erupt at the December elections as the threats arise that politicians who were responsible for the independence vote could face treason charges.
In a televised address, Carles Puigdemont appealed for Catalan citizens to remain peaceful and use “democratic opposition” to advance their cause.
He said: “Let’s move forward with the only winning attitude — without violence, insults, in a very inclusive way, respecting opinions and symbols and protests by other people who are against what the parliamentary majority decided.”
As he called on fresh elections to “restore normality”, Prime Minister Rajoy said: “We have decided to sack the Catalan government.
“Central government will assume the powers of the Catalan administration.”
It comes as the senior lecturer in Hispanic and Catalan Studies at the University of Bristol, Dr Sally-Ann Kitts, said: “The civil guard and the national police never left Catalonia.
“They will be deployed and meet with large groups of Catalan people providing peaceful resistance.”
“The images we saw on October 1, people standing with their hands up in this sort of stand-off, and eventually the guards charged forward riot shields and batons – I really will be amazed if we don’t see more of that, sadly.”
The declaration of independence was criticised by world leaders including Theresa May, who has said that Britain “will not recognise’ Catalan independence.