Brussels prosecutors said all five were taken into custody to start the process of their possible extradition to Spain.
They had fled to Belgium this week after being removed from power by Spanish authorities as part of an extraordinary crackdown to impede the region's illegal declaration of independence.
"This morning the five people wanted by Spain presented themselves to police in Brussels. They were put in custody at 9.17 this morning," Gilles Dejemeppe, a spokesman for Brussels prosecutors, told a news conference.
"The judge will hear the people this afternoon. He has until tomorrow morning to decide."
If the judge decides to issue an arrest warrant on the basis of the Spanish request, the case then goes to a court which must decide within 15 days whether to execute the order.
Mr Puigdemont can appeal at various stages of the proceedings, a process which can take many weeks.
The delay could giveMr Puigdemont time to participate, albeit from afar and in largely a symbolic capacity, in the snap regional election called by Spain's government for Catalonia on 21 December.
A Spanish National Court judge issued warrants for the five separatist politicians on suspicion of five crimes, including rebellion, rebellion and embezzlement, on Friday, a day after the same judge sent another eight former Catalan Cabinet members to jail without bail while her investigation continues. A ninth spent a night in jail and was freed after posting bail.
The separatist majority of Catalonia's Parliament ignored repeated warnings from Spanish authorities and voted in favour of a declaration of independence on 27 October.
The next day, Spain's central government used extraordinary constitutional powers to fire Catalonia's government, take charge of its administrations, dissolve its regional parliament and call a regional election.
Spain's Constitution says the nation is "indivisible" and that all matters of national sovereignty pertain to the country's parliament.
In all, Spanish prosecutors are investigating 20 regional politicians for rebellion and other crimes that could be punishable by up to 30 years in prison.
Another two leaders of pro-secession grassroots groups are also in jail while an investigation continues into suspicion of sedition.
Hundreds of pro-secession Catalans gathered in town squares across the region Sunday to put up posters in support of independence and to demand the release of the jailed separatists.
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