The A-380 would operate daily to both Mumbai and New Delhi with effect from 30 May, 2014, taking over from two daily flights that currently serve each city using the smaller Boeing-777s.
Another daily flight would continue to be operated with B-777s. In total, 14 flights would serve each city per week, an airline statement said.
While SIA's B-777s offer over 330 seats in a three-class configuration, the A-380s have a total seat capacity of 471.
"We have been keen to operate the Airbus A380 to India and are glad that the Air Services Agreement between Singapore and India now allows us to do so," said Singapore Airlines' (SIA) Senior Vice President Marketing Planning Ms Lee Wen Fen.
"India is a particularly important market for Singapore Airlines and we are very pleased that more of our customers will soon be able to experience the spaciousness and comfort of the world's largest aircraft," she said.
SIA's General Manager (India) David Lau said his airline was the first in the world to operate the A-380. "The SIA's A380 not only has immense public appeal but also showcases our commitment to offer the best in-flight experience to Indian travellers."
He said Indian customers would now be able to enjoy the complete A-380 experience from Delhi and Mumbai to our onward A-380 destinations including Frankfurt, Hong Kong, London, Los Angeles, Melbourne, New York, Paris, Shanghai, Tokyo Narita and Zurich.
Late January, government had cleared the deck for A-380 operations from Delhi, Mumbai, Hyderabad and Bangalore, lifting a five-year-old ban.
The restriction, which was lifted by Civil Aviation Ministry after several years of demands by these major foreign carriers, was imposed in 2008 as the government then felt these double-decker, wide-body and long-haul jets would help foreign airlines to take away a large chunk of global traffic which could be detrimental to the Indian carriers' interests.
Delhi and Mumbai airports have received DGCA certification and are making preparations to receive the superjumbos in terms of various services required to handle the large number of passengers these planes can accommodate when they land or take off.
Commenting on the decision, Delhi International Airport CEO I P Rao said the scheduled A380 service connecting Delhi to Singapore daily "demonstrates Delhi's emergence as a true world-class airport, supporting the world's largest passenger commercial aircraft."
Mumbai International Airport CEO Rajeev Jain said the A380 operations "further demonstrates Mumbai's emergence as a world-class airport, which now supports routes to established and emerging markets across the globe.