Mr Puigdemont and the former-ministers had fled to Belgium after being removed from power by Spanish authorities as part of an extraordinary crackdown to impede the region’s declaration of independence, which Spain views as illegal.
Belgian prosecutors, who have a European arrest warrant from Spain for Mr Puigdemont and four of his associates, have said they will brief media on the case.
They said five people want by Spain had been taken into custody.
A spokesman for Brussels prosecutors Gilles Dejemeppe said: “This morning the five people wanted by Spain presented themselves to police in Brussels.
“They were put in custody at 9.17am this morning.

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“The judge will hear the people this afternoon. He has until tomorrow morning to decide.”
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 earlier the same judge jailed another eight former Catalan Cabinet without bail while her investigation continues. A ninth spent a night in jail and was freed after posting bail.
Mr Puigdemont wrote in Dutch in his Twitter account on Saturday that he is “prepared to fully cooperate with Belgian justice following the European arrest warrant issued by Spain”.
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.