He tapped Catalan lawmaker Quim Torra to take the helm, urging parliament to confirm him as regional president.
Separatist parties in Catalonia are backing the former head of a pro-independence group to become the Spanish region's new president.
In a widely shared video on social media, Puigdemont suggested Quim Torra for president, signalling a potential end to months-long wrangling over a new regional government.
If he is elected to office, he must form a regional government with the intention of leading Catalonia's independence movement.
Spain's constitutional court on request of the Spanish government decided that the approval of the home government the candidate must be present to vote in person.
However, Mr Torra could still be elected in a second round of voting to be held on Monday in which only a simple majority in the 135-seat regional parliament is needed, provided the far-left CUP party can be persuaded not to vote against his candidacy.
But he did say he was "ready to talk tomorrow without conditions" with the government of Spanish Prime Minister Mariano Rajoy in Madrid.
Rajoy quickly responded to the speech, saying: "What we saw and heard did not please us. but we will judge his actions".
Other leaders of the Together for Catalonia Party also face charges of rebellion.
Since Catalonia's last election in December, four attempts to form a government have failed because the presidential candidates were either in self-imposed exile or in custody. No date has been set for a vote in the Catalan parliament, where separatist parties have a slender majority.
The central government in Madrid has been managing Catalan public affairs since shortly after separatist politicians made an independence declaration last October based on the results of an outlawed referendum on secession.
Catalonia has been in political limbo since December a year ago when pro-independence parties won early elections.