But there are obstacles in Madrid's way, given that Catalans are fiercely protective of their region's high degree of autonomy, such as direct control over education, healthcare and the police.
Only nine percent of civil servants in Catalonia -- 26,000 people -- come directly under the orders of the central administration.
That's far less than in the southern region of Andalusia (19 percent) and Madrid (39 percent).
According to the El Pais daily, for instance, the state only has 5,900 security forces under its direct control. Which explains why it had to dispatch some 10,000 national police and Guardia Civil forces to the region during the separatist crisis.
Deposing the regional government
That could prove a headache for Prime Minister Mariano Rajoy.
What will he do, for instance, if Puigdemont, who has already defied the state with a banned independence referendum, refuses to leave his office?
"He would be committing more offences," says a government source in Madrid.
The source, who refused to be named, added that any decision to evict him -- and even detain him if he is accused of an offence like rebellion -- would have to be taken by a judge and implemented by Catalan police.
In this 7.5-million-strong region about the size of Belgium, Catalans are protective of their autonomy and independence supporters used to taking to the streets.
A civilian collective called "Stand up for peace" has already distributed instructions for a "non-violent strategy of liberation".
They could launch strikes or boycotts.
Of the 304,000 civil servants in Catalonia, 167,000 work for the regional administration, and 84,000 for town or city halls.
Some of these could be reluctant to obey orders from Madrid.
Spain's Deputy Prime Minister Soraya Saenz de Santamaria has warned there could be "dismissals of employees who continue to overtly disrespect the constitution".
Ramon Font, spokesman for the Ustec teachers union in Catalonia, said members would "not recognise an administration that doesn't stem from" from Catalan elections.
Firefighters are also determined to resist. "If a road is blocked (by protesters) and we get asked to unblock it, it's probable we won't respond," one firefighter told AFP, wishing to remain anonymous.
Another obstacle is taking control of the Mossos d'Esquadra, Catalonia's police.
"It wouldn't go down well if a (national) police officer or someone from outside came to take control of the Mossos," acknowledges Ramon Cosio, spokesman for the SUP national police union.
One positive point for Madrid -- it already has control of much of Catalonia's cash, after seizing control of wide areas of Catalan public spending in September, seeking in vain to stop the referendum.