"I am not here in order to demand asylum," Puigdemont, sacked by the Spanish government on Friday after Catalonia's parliament declared independence, told a packed news conference in Brussels.
He said he was in Belgium "for safety purposes and freedom", without detailing how long he would stay.
After being axed, the 54-year-old reportedly drove hundreds of kilometres from Catalonia to Marseille in southern France with several members of his dismissed cabinet and then flew to Belgium.
On October 1, Catalonia held a referendum organised by Puigdemont's administration which it said saw a large majority vote in favour of seceding from Spain, although turnout was just 43 per cent.
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Puigdemont said this gave the Catalan parliament a mandate to declare independence on Friday, a decision beamed onto big screens to cheering crowds in regional capital Barcelona.
But the same day Spanish Prime Minister Mariano Rajoy's government in Madrid invoked a never-before-used article of the constitution to dismiss Catalonia's leaders and impose direct rule.
On Monday Spain's chief prosecutor said he was seeking charges including rebellion -- punishable by up to 30 years in prison -- and sedition against Puigdemont and fellow leading separatists.
Jose Manuel Maza said they had "caused an institutional crisis that led to the unilateral declaration of independence carried out on October 27 with total contempt for our constitution".
A court now has to decide whether to bring charges.
Separately, Spain's Civil Guard police force on Tuesday searched the headquarters of Catalonia's regional police in a probe centred on the independence referendum, a spokesman said.
With its own language and distinct culture, Catalonia accounts for a fifth of the eurozone country's economy.
It had a high degree of autonomy over key sectors such as education, healthcare and the police.
Rajoy also called snap elections for December 21 to replace the Catalan parliament in a drastic bid to stop the secessionist drive.
Puigdemont said on Tuesday that he accepted the "challenge" and that he would "respect" the result whatever it is.
"I want a clear commitment from the state. Will the state respect the results that could give separatist forces a majority?" he nevertheless asked reporters in Brussels.
Catalan police, now under orders from Madrid, were told Monday they could allow the dismissed leaders to enter the government headquarters in Barcelona, but only to clear their desks.
But in the end, apart from one regional minister who tweeted a photo of himself at his desk, there was no major resistance.
On Monday Joan Escanilla from the CSIF civil servants union said: "For now everything is very quiet. People have returned to work as normal.