The government said ministers would meet to activate Article 155 of the constitution, allowing it to take over running of the region.
Carles Puigdemont said earlier the Catalan parliament would vote on independence, backed in a disputed referendum on October 1, if Spain “continues repression”.
Some fear the moves could spark unrest.
The government statement said: “The Spanish government will continue with the procedures outlined in Article 155 of the Constitution to restore legality in Catalonia’s self-government.
“It denounces the attitude maintained by those in charge of the Generalitat [Catalan government] to seek, deliberately and systematically, institutional confrontation despite the serious damage that is being caused to the coexistence and the economic structure of Catalonia.
“No-one doubts that the Spanish government will do all it can to restore the constitutional order.”
Article 155 of Spain’s 1978 constitution, which cemented democratic rule after the death of General Franco three years earlier, allows Madrid to impose direct rule in a crisis but it has never been invoked.
Political leaders in Madrid and Barcelona, Catalonia’s capital, have been engaged in a tense stand-off since the disputed referendum, which Catalan leaders say resulted in a “Yes” vote for independence but which Spain’s supreme court regards as illegal.
Spain’s PM Mariano Rajoy set the deadline of 10:00 local time for Carles Puigdemont to offer a definitive answer on the independence question, and called on him to “act sensibly”.
The prime minister said in parliament on October 18: “It’s not that difficult to reply to the question: has Catalonia declared independence? Because if it has, the government is obliged to act in one way, and if it has not, we can talk here.”
This was the second and final deadline, as Madrid says Carles Puigdemont on October 16 failed to clarify whether he had declared independence.
PM Mariano Rajoy is due to attend an EU summit in Brussels on October 19.
On October 21, the government will be expected to draw up a list of specific measures under Article 155 of the constitution, launching the transfer of powers from Catalonia to Madrid.
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