Eight former members of the Catalan government are being kept in custody while they're investigated on possible charges of rebellion and misuse of funds.
Judge Carmen Lamela ordered the ministers to be jailed unconditionally.
Their lawyers, who plan to appeal the move, said those detained were "serene" and wanted the people of Catalonia to stay calm.
Jaume Alonso-Cuevillas, representing five of them, said Thursday's decision "lacked justification" and was "disproportionate".
The Supreme Court adjourned hearings into former members of the Catalan parliament until November 9th to give them time to prepare a defence.
Twenty seccessionist leaders were summoned to two courts in Madrid to answer questions, but only 15 turned up.
Spain's state prosecutor has also asked for a European arrest warrant to be issued for the region's sacked leader Carles Puigdemont.
He's currently in Belgium.