There was instant chemistry between Li and Rodriguez last week when the 30-year-old Chinese won the Cincinnati WTA crown, her first title since her landmark French Open victory in 2011.
"We have had a very good beginning," said Li, the world number nine, who had endured an on-off coaching relationship with husband Jiang Shan.
"I feel more comfortable working with him, more relaxed, less stressful. I trust Carlos. Husband is husband and coach is coach. Otherwise, it's too tough for my mind."
Li, whose best performance at the final Grand Slam event of the season remains her quarter-final run in 2009, lost to Romanian teenager Simona Halep in the first round last year.
She admitted then that she was wilting under the pressure of expectation from her legion of Chinese fans, claiming she felt she was walking around with a "target" on her back.
But she has been rejuvenated by her win in Cincinnati and by her new partnership with Rodriguez, who brings his own insight into the China mindset having set up a tennis academy in Beijing.
Rodriguez put in 15 years with Henin as the Belgian won seven Grand Slam titles.
Li said that she realized changes were needed after Wimbledon, where she lost as third seed to German Sabine Lisicki in the second round.
"I texted my agent and said I need a new coach," she explained. "Two weeks later, my agent said, 'Oh we have one coach.' I said, 'Perfect, I need him.' Of course I know him. I was so surprised he also wanted to help me.
"I asked many coaches and they said, 'Oh, he's a very positive person. He has good communication with the players.' I need this right now."
Li will be Asia's most realistic hope of making progress at the US Open.
China's world 32 Zheng Jie has yet to get beyond the third round while Peng Shuai, the world 36, reached the fourth round in 2011.
However, Peng goes into the tournament, which starts on Monday, under a fitness cloud having pulled out of the Dallas warm-up tournament this week with a shoulder injury.
Taiwan's challenge will be led by Hsieh Su-Wei, the world number 57, while Japan's women's tennis is in a slump with their highest-ranked player Ayumi Morita standing at 94.
In the men's singles, Japan's world number 18 Kei Nishikori will be seeded.
He was a quarter-finalist at the Australian Open and the Olympics this year but was a second round casualty at the US Open in 2011 when he retired from his second round clash with Italy's Flavio Cipolla with a back injury.
In 2010, a groin injury forced him out of his third round tie with Albert Montanes.
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