They were poised to possibly arrest the Catalan leader if he had made a clear declaration of independence last night.
When asked for a statement regarding Rajoy's statement, Catalan government spokesman Jordi Turull said that should Madrid invoke Article 155, the Catalan government would press on with its independence.
Addressing the Catalan Parliament in Barcelona, Puigdemont said the autonomous region had won the right to be independent as a result of the vote.
And now the prime minister of Spain is demanding that he clarify whether Catalonia is declaring independence.
FRAYER: "I propose we suspend the effects of this declaration of independence", he said, "so that in the coming weeks, we may begin a dialogue".
But Spain's political establishment rounded on Puigdemont following his declaration, and support among separatists in Catalonia was mixed.
There is no suggestion that the crisis could degenerate into an armed conflict but it could damage the region and Spain as a whole economically, bringing new instability to the eurozone.
Deputy prime minister Soraya Saenz de Santamaria told reporters shortly after the signing that Puigdemont was "a person who doesn't know where he is, where he's going or with whom he wants to go".
In Brussels, there was a sense of relief that the euro zone's fourth-largest economy now had at least bought some time to deal with a crisis that was still far from over.
Ahead of Puigdemont's address on Tuesday, influential figures including Barcelona's Mayor Ada Colau and European Council President Donald Tusk had urged him to step back from declaring independence. And French President Emmanuel Macron rejected Puigdemont's call for European Union mediation, saying he was confident Madrid could handle the situation.
One EU official said Puigdemont "seems to have listened to advice not to do something irreversible".
Nearly 90% of voters backed independence with a turnout of 43%, Catalan officials say.
Spain has been in turmoil since the separatist government held a disputed referendum in Catalonia on 1 October which was declared invalid by the country's Constitutional Court.
Rajoy said on Wednesday after an emergency cabinet meeting that Madrid would do everything possible to prevent Catalonia from seceding.
The stakes are high - losing Catalonia, which has its own language and culture, would deprive Spain of a fifth of its economic output and more than a quarter of exports.