The inaugural edition of the IPTL takes place later this year with matches in Bangkok, Mumbai, Singapore and Dubai geared to raise the profile of the game across Asia and the Middle East.
But the event, modelled on cricket's financially successful Indian Premier League, has been dealt a blow by the absence of Asia's top male and female players -- Japan's Kei Nishikori and second-ranked Li.
The Chinese star became Asia's first Grand Slam winner at the 2011 French Open and followed it up with a second major title at Melbourne in January, propelling her to a career-high rankings position.
Women's Tennis Association (WTA) chief Stacey Allaster has placed the 32-year-old at the head of a concerted push into Asia including multiple new tournaments in China and the end-of-season championships in Singapore.
In September, Li's home city of Wuhan will host a new, premier-level competition, one of six WTA events on Chinese soil this year.
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But the current hottest property in women's tennis appears to have no room in her tightly-packed calendar for November and December's IPTL -- the brainchild of Indian doubles star Mahesh Bhupathi.
"I already put my schedule (together) at the end of last year," Li told a press conference in Hong Kong, where she was due to play an exhibition match against former US Open champion Samantha Stosur to mark World Tennis Day.
"When I was doing it I didn't see any (IPTL) tournament... so that's why I didn't do (schedule) it."
Stosur later beat Li in two sets to win the match 6-4, 6-3.
The much-talked-about league will take place during the off season in the tennis calendar, between November 27 and December 14, and will feature 24 matches across the four host cities.
It falls at a time when most tour players opt to get some rest and will come just weeks before Li would be due to defend her Australian Open title in January.
The team event will take place shortly after October's season-ending WTA Championships in Singapore, which, barring any mishap, Li will contest as one of the world's top eight players.
Li told reporters in the southern Chinese city that her focus was on adding to her two Slams and replacing Serena Williams at the top of the rankings.
"I want to be number one in the world," she said. "It's a goal, the dream for all athletes. I will try as hard as I can. There's no timing (put on it)."
Li said she was handling the aftermath of her second Slam win better than her first when she struggled to deal with the pressure of expectation and suffered a slump which led her to even consider retirement.
"After I won the French Open I didn't have any experience and also nobody told me what I should do next," she said.
"This time it's different. I'm working with (coach) Carlos (Rodriguez) and he has a lot of experience. He told me before what I should do."
Russia's Maria Sharapova and Swiss great Roger Federer are also missing the IPTL in which $23,975,000 has been spent signing up players including Novak Djokovic, Rafael Nadal and Williams.
World number five Tomas Berdych and former top-ranked Lleyton Hewitt will play for Team Singapore while Wimbledon champion Andy Murray lines up for Team Bangkok.
Each match will follow a best-of-five format comprised of separate sets contested in men's singles, women's singles, men's doubles, mixed doubles and past champions singles.
"It's an honour to be picked," Berdych told AFP in Hong Kong Monday ahead of his exhibition match with Hewitt. "I'm always looking for a new experience and I see this is a good one. I think it's going to be a great success."
Hewitt said it was a "fantastic concept".
Hewitt later beat Berdych, winning 6-4, 7-5.