The move comes after Belgium's asylum and migration affairs minister Theo Francken said the former president could seek asylum in the country.
The Spanish media reports that the former leader is accompanied by an unspecified number of other members of the Catalan government.
The group are expected to make a joint statement later today.
Spain's prosecutor José Manuel Maza said on Monday morning that rebellion, sedition, and provocation charges would be levelled at the former leaders of the Catalan government, which has been suspended by the Spanish central government in Madrid.
In accordance with Spanish law a judge will not assess the charges.
Spain has refused to recognise the result of an independence referendum held by Catalonia's regional government at the start of the month on the basis that it is illegal under Spanish law.
After the Catalan regional parliament voted to declare independence on Friday, the Spanish government said it would revoke the region's autonomy and rule it directly from Madrid.
Catalonia referendum protests – in pictures
Catalonia referendum protests – in pictures
1/10
Demonstrators block a Guardia Civil vehicle as they try to leave the Department of External Affairs, Institutional Relations and Transparency of the Catalan Government office in Barcelona
AP/Emilio Morenatti
2/10
Demonstrators react as they try to stop the car carrying Xavier Puig, a senior at the Department of External Affairs, Institutional Relations and Transparency of the Catalan Government office, after he was arrested by Guardia Civil officers in Barcelona
AP/Emilio Morenatti
3/10
A demonstrator reacts as he tries with others to stop the car carrying Xavier Puig, a senior at the Department of External Affairs, Institutional Relations and Transparency of the Catalan Government office, after he was arrested by Guardia Civil officers in Barcelona
AP/Emilio Morenatti
4/10
Spokeswoman of the Catalan pro-independence anticapitalist party "Candidatura d'Unitat Popular - CUP" (Popular Unity Candidacy), Ana Gabriel, talks to the media in Barcelona
Josep Lago/AFP
5/10
Republican Left of Catalonia party's (ERC) Member of Parliament Joan Tarda (C) attends a demonstration outside the regional Economy Ministry in Catalonia during a police search for documents connected with the organisation of the Catalan independence referendum, in Barcelona
EPA/Alejandro Garcia
6/10
A man holds pro-referendum poster next to a Spanish Civil Guard who stands in front of the Economy headquarters of Catalonia's regional government in Barcelona. The operation comes amid mounting tensions as Catalan leaders press ahead with preparations for an independence referendum on October 1 despite Madrid's ban and a court ruling deeming it illegal
Josep Lago/AFP
7/10
People hold placards reading "Democracy" as they protest in front of the Economy headquarters of Catalonia's regional government in Barcelona
AFP
8/10
A crowd of protesters gather outside the Catalan region's economy ministry after junior economy minister Josep Maria Jove was arrested by Spanish police during a raid on several government offices, in Barcelona
Reuters/Albert Gea
9/10
People holding 'Esteladas' (Catalan pro-independence flags) attend a protest near the Economy headquarters of Catalonia's regional government
Lluis Gene/AFP
10/10
People demonstrate on a Spanish Civil Guard Police car outside the Catalan Vice-President and Economy office as police officers holds a searching operation inside
David Ramos/Getty Images
1/10
Demonstrators block a Guardia Civil vehicle as they try to leave the Department of External Affairs, Institutional Relations and Transparency of the Catalan Government office in Barcelona
AP/Emilio Morenatti
2/10
Demonstrators react as they try to stop the car carrying Xavier Puig, a senior at the Department of External Affairs, Institutional Relations and Transparency of the Catalan Government office, after he was arrested by Guardia Civil officers in Barcelona
AP/Emilio Morenatti
3/10
A demonstrator reacts as he tries with others to stop the car carrying Xavier Puig, a senior at the Department of External Affairs, Institutional Relations and Transparency of the Catalan Government office, after he was arrested by Guardia Civil officers in Barcelona
AP/Emilio Morenatti
4/10
Spokeswoman of the Catalan pro-independence anticapitalist party "Candidatura d'Unitat Popular - CUP" (Popular Unity Candidacy), Ana Gabriel, talks to the media in Barcelona
Josep Lago/AFP
5/10
Republican Left of Catalonia party's (ERC) Member of Parliament Joan Tarda (C) attends a demonstration outside the regional Economy Ministry in Catalonia during a police search for documents connected with the organisation of the Catalan independence referendum, in Barcelona
EPA/Alejandro Garcia
6/10
A man holds pro-referendum poster next to a Spanish Civil Guard who stands in front of the Economy headquarters of Catalonia's regional government in Barcelona. The operation comes amid mounting tensions as Catalan leaders press ahead with preparations for an independence referendum on October 1 despite Madrid's ban and a court ruling deeming it illegal
Josep Lago/AFP
7/10
People hold placards reading "Democracy" as they protest in front of the Economy headquarters of Catalonia's regional government in Barcelona
AFP
8/10
A crowd of protesters gather outside the Catalan region's economy ministry after junior economy minister Josep Maria Jove was arrested by Spanish police during a raid on several government offices, in Barcelona
Reuters/Albert Gea
9/10
People holding 'Esteladas' (Catalan pro-independence flags) attend a protest near the Economy headquarters of Catalonia's regional government
Lluis Gene/AFP
10/10
People demonstrate on a Spanish Civil Guard Police car outside the Catalan Vice-President and Economy office as police officers holds a searching operation inside
David Ramos/Getty Images
Belgian asylum minister Mr Francken hails from the Flemish nationalist party New Flemish Alliance, which has close ties to the Catalan separatist movement.
His party advocates an independent Flanders and wants it to secede from Belgium.
“Catalan people who feel politically threatened can ask for asylum in Belgium. That includes President Puigdemont. This is 100 percent legal,” Mr Francken told Belgian public broadcaster VRT at the weekend.
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