Gilberto Kassab told reporters that the construction of the Itaquerao, the start of which has been repeatedly put off, should finally get under way in April barely three years before the tournament will take place.
"We can say that without question we will have the World Cup opening match in Sao Paulo, in Itaquera, in the stadium of Corinthians," Kassab told reporters.
The Sao Paulo venue is the biggest of many headaches facing the 2014 World Cup hosts where initial worries about crumbling infrastructure and rampant crime have been exacerbated by delays in the building or reconstruction of stadiums.
Sao Paulo initially planned to use the Morumbi stadium until the arena was barred by FIFA and local organisers over a lack of financial guarantees for the necessary rebuilding.
Kassab met with Brazil President Dilma Rousseff and state governor Geraldo Alckman on Friday to discuss the matter.
"The president invited the mayor and governor to this meeting because her perception is that Sao Paulo is the city which must have the opening match, thanks to its infrastructure, hotels and the quality of its services," said sports minister Orlando Silva.
The stadium will be situated in the east of the sprawling city, several kilometres from the centre.
Corinthians, one of Brazil's biggest and most popular clubs, had planned to built the stadium with a capacity of 48,000, while FIFA require a minimum of 65,000 for the opening match.
Negotiations are taking place over who will pay for the building of the extra 17,000 seats.
Brazil was elected unopposed in 2007 to host the tournament which was earmarked for South America by FIFA under a short-lived rotation system which also brought last year's World Cup to Africa.
Brazil is due to stage the tournament in 12 cities despite the difficulties of moving around the vast country.
Last November, sports minister Silva said that the country's outdated and overcrowded airports were the biggest risk to the event's success and that not enough was being done to improve them.
