According to Spain's chief prosecutor, the Catalan leaders were accused of rebellion - which carries a maximum 30-year jail term - as well as sedition and misuse of funds.
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.
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"When someone doesn't appear after being cited by a judge to testify, in Spain or any other European Union country, normally an arrest warrant is issued", Supreme Court President Carlos Lesmes said, according to Reuters.
An arrest warrant would make it virtually impossible for Mr Puigdemont to stand in a snap election, called for 21 December, after the Catalonian government was dissolved by Spain in light of the vote for independence.
An investigation could take years before it leads to a trial.
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Catalan President Carles Puigdemont, meanwhile, is in Brussels with ministers Meritxell Serret, Toni Comin, Clara Ponsati and Lluis Puig. Ninety percent of voters were in favor of separating from Spain.
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. With Puigdemont and four others in Belgium, only 15 turned up.
A Spanish judge has jailed eight ousted Catalan ministers, after the region attempted to declare independence.
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The Supreme Court adjourned hearings into former members of the Catalan parliament until 9 November to give them time to prepare a defence.
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