At 39, Paes has had a good run in 2012 winning four titles, including the Australian Open (doubles) and reaching the finals at Tokyo and US Open.
And for the 29-year-old Frenchman, the year has brought three doubles titles, taking him to a career-best doubles ranking of 38. He, though, will finish the year at 43.
This is the first time the duo will partner each other in a tournament in which the Indian had won six times in 17 appearances.
"Paes and Roger-Vasselin are pairing up for the first time at the 2013 edition of the Aircel Chennai Open. While enough has been written and said about Leander, it will be a tremendous learning opportunity for Roger-Vasselin," said tournament director Tom Annear.
"Going by their individual records and playing styles, I am pretty certain the duo will give the others a run for their money in this tournament," he added.
Among other Indian players, world No. 11 Mahesh Bhupathi will play alongside world No. 5 Daniel Nestor while the number 12 ranked Rohan Bopanna will be pairing up Rajeev Ram in the event.
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Karti P Chidambaram, tournament organising committee chairman and AITA vice-president said, "It is always a pleasure to have Leander Paes playing in Chennai. Besides him being a fine doubles player, he is also the most successful here with six titles under his belt.
The tournament already has four doubles players from the top 20, with two of them ranked among the top ten.
India's only ATP World Tour tennis event will take place in the city's SDAT Tennis Stadium from December 31, 2012 to January 6, 2013.