Spain's High Court on Tuesday summoned sacked Catalan leader Carles Puidgemont and 13 other members of his dismissed government to appear later this week.
It also gave them three days to pay a deposit of €6.2 million ($7.2 million) to cover potential liabilities.
The summons comes after Spain's chief prosecutor on Monday said he would press charges including rebellion.
Mr Puigdemont is in Belgium with several former ministers. He earlier said he was not there to seek asylum.
Carles Puigdemont triggered a crisis in Spain by holding an independence referendum in early October in the semi-autonomous region despite Madrid's opposition and the Constitutional Court declaring the vote illegal.
Spain's central government has now taken direct control of Catalonia.
Mr Puigdemont turned up in Brussels on Monday as Spanish Attorney-General José Manuel Maza called for Catalan leaders to face charges of rebellion, sedition, and misuse of public funds.
The Audiencia National has now summoned the sacked Catalan officials - who are yet to be formally charged - to testify on Thursday and Friday. If they do not appear, prosecutors could order their arrest.
Meanwhile, the speaker of Catalan's dissolved parliament Carme Forcadell and other former lawmakers have been summoned to the Supreme Court because they still have parliamentary immunity.
Mr Puigdemont earlier said he would return to Spain if guaranteed a fair hearing.
Several of Mr Puigdemont's former colleagues who remain inside the country may decide to accept the summons and appear in court, reports the BBC's James Reynolds from Barcelona.
The charge of rebellion carries a maximum 30-year jail term.