It appears likely that a European arrest warrant is now likely to be made by a High Court judge.
Prosecutors had asked the judge to detain eight of the nine former government members who turned up for questioning in Madrid, accused of rebellion, sedition and misuse of public funds.
This came after Catalan lawmakers voted to declare independence of the affluent north-eastern region.
The deposed leader was photographed in a cafe in Brussels on Thursday while other Catalan government members appeared in court.
Mr Puigdemont's lawyer in Belgium said his client would stay away from Spain while the political climate was "not good"; but he would cooperate with the courts.
"We have to admit that because this is a very special case it could pose political questions", said Maxime Chome, a lawyer and legal expert at Brussels Free University.
The eight include former Catalan vice president Oriol Junqueras.More news: Suspect arrested in carjacking that killed Chinese student in Utah
Last week, Spanish Prime Minister Mariano Rajoy imposed direct rule on Catalonia, dissolving the regional parliament and calling snap local elections.
The crimes being probed are punishable with up to 30 years in prison under Spanish law.
Another, Santi Vila, who stepped down from the Catalan cabinet before a unilateral declaration of independence last Friday and has since then been pushing for a negotiated solution with the government, was granted bail of €50,000.
They include regional parliament speaker and prominent pro-independence activist Carme Forcadell, and 14 ousted Catalan government ministers including Mr Puigdemont.
One challenge, Chome said, is to decide what type of offenses and charges will be listed in the warrant, as Belgium does not have the equivalent charges of sedition and rebellion that Puigdemont and his associates could face.
The Supreme Court said the hearing of the six regional parliament board members was postponed until November 9 following a request by their lawyers.