Just two weeks after Spain's parliament overwhelmingly shot down the referendum bid, Mas said he was determined to hold a vote.
"The referendum will be called for sure and the Catalan people will be called to the polls on November 9th," he told foreign correspondents on the day the region celebrates its patron Sant Jordi, or Saint George.
"Might the central government want to cancel it? I don't know. That doesn't depend on me," Mas said.
Mas also send letters to civil servants in Catalonia, telling them "2014 will be the year Catalonia votes", Spain's El Mundo newspaper reported on Thursday.
"I hope, desire and trust that we will exercise our rights in an exemplary fashion and that we will do it with full respect for everyone's opinions," the letter to all public workers read, according to the national daily.
The planned referendum would ask voters two questions:
– "Do you think that Catalonia should be a State, yes or no?"
– "If yes, do you want that State to be independent, yes or no?"
Many Catalans point to Scotland, whose leaders have called a referendum to be held in September on independence from Britain — a move authorized by the British government.
But Prime Minister Mariano Rajoy has vowed to block any referendum.
With both the ruling Popular Party and the main opposition Socialist Party against the referendum, Spain's parliament rejected the bid by 299–47 votes on April 8.
Nevertheless, the Catalan government says it will now seek to pass a regional law allowing it to conduct a consultative referendum on the question.
Mas urged the Spanish government not to block such a vote, which he has promised to hold since winning November 2012 regional elections.
"We ask that it not obstruct a process that will be strictly Catalan, with a Catalan law approved by the Catalan parliament," he added.
"It will not be strictly binding, it will be purely participatory to find out the opinion of the Catalans."
We will not stop
Proud of their distinct language and culture, a growing number of Catalonia's 7.5 million citizens resent the redistribution of their taxes to other parts of Spain and believe the region would be better off on its own.
The 2008 real estate crash that triggered a five-year economic downturn across Spain has added to the pressure for secession over the past two years.
Polls indicate a slim majority of Catalans support independence.
Spain's prime minister has promised to appeal against any referendum to the nation's Constitutional Court, however.
Rajoy says Spain is better off united and that a referendum would flout the country's 1978 constitution, which confers sovereignty on all Spaniards, not those of a single region.
The Constitutional Court ruled last month that a region like Catalonia could not "unilaterally" call a referendum on its sovereignty.
But Mas was undeterred.
"The offer of dialogue is permanent and remains open but we will not stop the process. If we stop and there is no alternative, the frustration will be total and absolute," he said.
The Catalan political chief has previously promised to act within the law.
Mas has said, too, that if the referendum is frustrated he could call snap elections as a form of plebiscite on the future of Catalonia.