The friendly between the South American rivals, in the buildup to 2014 FIFA World Cup qualifiers, will be the biggest football match ever in a country where cricket's dominance has long been felt. But football does thrive in the match venue of Kolkata, formerly Calcutta. The city has a rich tradition of club competition, and excitement in and around the Salt Lake stadium - the largest in India - is building.
"It will be a memorable day for Kolkata as it will witness a few great players live in action during their peak years," said Bhaswar Goswami, whose company brokered the deal that brought Argentina to India.
Thousands of fans waited at Kolkata airport for Messi's arrival early Wednesday, but he slipped past the chanting crowds without being spotted. While cricket is undoubtedly India's first sporting love, the fast-developing country of 1.2 billion people is a huge potential football market with more and more middle-class viewers tuning into satellite TV.
English Premiership side Blackburn Rovers are now Indian-owned, and Liverpool are opening a coaching academy on the outskirts of New Delhi in October. Bayern Munich stopped by in Kolkata last year to play a charity match with top domestic side East Bengal, the German side's second visit in two years.
But India has never seen the likes of Barcelona superstars Messi and Javier Mascherano grace the field. After captaining the national side once at last year's FIFA World Cup, Messi will be starting his tenure as full-time skipper. "Messi is loved by millions of fans across the globe," said Argentina's assistant coach Julian Camino, after the striker was handed the captain's armband by new coach Alejandro Sabella, in place of Mascherano.
"He's aware that he will be well-received by his fans here too," said Camino, a former Argentina right-back who had a brief stint as a player with East Bengal in 1988. "He's the captain of the side and he's pretty excited about coming here. We hope the stadium will be packed and it will be a memorable match."
Argentina, hoping to build up a loyal following across south Asia, head after Kolkata for a friendly on 6 September against Nigeria in Dhaka, the capital of Bangladesh - already a hotbed of football fever.
While the 24-year-old Messi will be the centre of attention, his team will look to start afresh after a disappointing performance in the Copa America at home in July when they lost to eventual winners Uruguay in the quarter-finals. The Copa failure cost Sergio Batista his job as national coach and led to the appointment of Sabella, who was assistant Argentina coach from 1994 to 1998 and led Estudiantes to the Copa Libertadores in 2009.
Sabella signalled he meant business by dropping Manchester City forward Carlos Tevez from the squad to face both Venezuela and Nigeria. "It is an extremely important match both for me and the team," Sabella said. "There are huge expectations from us back home and it is a big responsibility. Venezuela are a good side and we will be approaching the match with utmost seriousness."
Venezuela go into the contest on the back of their best-ever showing in the Copa America, reaching the semi-finals where they only went out to Paraguay on penalties. The Venezuelans, ranked 44th in the world to Argentina's 9th - India are 158th - will also be keen to avenge a 4-1 away friendly defeat to the former world champions in March.