The Supreme Court had summoned five of the separatist leaders on Friday to rule on whether to remand them in custody as it opened the phase in the investigation that precedes a trial.
A total of 25 leaders are now set to be tried for rebellion, misuse of public funds and disobeying the state after last year's independence referendum and declaration.
Convictions could result in up to 30 years in prison.
Rovira, who did not specify where she was headed, is the seventh separatist to flee overseas to escape charges.Separatist parties won regional elections in December called by Madrid after they attempted to secede, retaining their absolute majority in parliament.
The four MPs of far-left party CUP demanded a clear path to build a Catalan independent republic | Marta Pérez EFE via EPA
Jordi Turull, a close ally of former president Carles Puigdemont, needed 69 votes to be elected but obtained only 64.
Recall that Catalonia declared independence from Spain in October 2017 after a political back-and-forth between the regional and national governments.
The decision was met with calls for demonstrations on the streets of Catalonia.
Along with him the Judge passed orders to to arrest without bail, all former regional legislators like Josep Rull, Raul Romeva and Dolors Bassa as well as the ex-president of the parliament, Carme Forcadell.
The five join four other Catalan leaders already detained in prison.
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Catalan parliament speaker Roger Torrent said on Friday he would continue with the session and read a statement in support of pro-independence leaders, despite opposition from the government and unionist parties in Catalonia.
The central government is now running Catalonia from Madrid. "Long live a Catalan Republic for all!", she said in a letter published in the Spanish media.
The separatist parties won regional elections in December called by Madrid after they attempted to secede, retaining their absolute majority in parliament.
The vote was boycotted by Catalans opposed to the region splitting from Spain.
The top court ruled that there was still a risk that Joaquim Forn, the ousted Catalan interior minister, and Jordi Sanchez, the former president of the pro-independence civil rights group ANC, to repeat the offences that landed them in jail.
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He was due to appear in court Friday along with several other leading separatists.
The separatist majority failed to elect a regional government in a Thursday vote.
But they have still not been able to form a government as their two previous candidates for the presidency proved problematic.
The semi-autonomous region has been without a leader for almost five months after central authorities took control following October's illegal independence declaration.
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