Spanish Prime Minister Mariano Rajoy also dissolved the regional parliament and called a new regional election to be held on December 21.
They came a day after one of the most tumultuous days in Spain's recent history, when Catalan lawmakers in Barcelona passed a declaration of independence Friday for the prosperous northeastern region, and the national parliament in Madrid approved unprecedented constitutional measures to halt the secessionist drive.
Plenary session of the Catalan Parliament.
Greece also expressed concern Saturday about Catalonia's independence bid, saying it supports Spain's territorial integrity.
The secessionists say a referendum on October 1 gave them a mandate for independence.
Greek government spokesman Dimitris Tzanakopoulos says "we are particularly concerned about the situation in Spain and repeat that Europe can only go forward united. unilateral actions cannot be accepted".
The Madrid government also sacked the Mossos' chief, Josep Lluis Trapero.
Spain's High Court barred Trapero from leaving the country and seized his passport as part of an investigation for alleged sedition, although it has not ordered his arrest.
Officials in Europe are speaking out against Catalonia's declaration of independence. But there was no trouble overnight and the streets were quiet on Saturday.
After Spain's central authorities made the takeover official early Saturday, Puigdemont and the 12 members who until Saturday made up the Catalan Cabinet are no longer paid. Demonstrations for and against independence continued late Friday night and more are expected on Saturday, with a rally "for the unity of Spain and the constitution" to be held in Madrid, the BBC reported. Shortly afterward, Spain's Senate gave the central government in Madrid the power to take direct control of the region and fire its separatist government.
The chaos has also prompted a flight of business from Catalonia, which contributes about a fifth of Spain's economy, the fourth-largest in the euro zone. European leaders have denounced the push, fearing it could fan separatist sentiment around the continent.