The 30-year-old has a good recent track record at Melbourne Park, reaching the 2010 semi-finals, losing the 2011 final to Kim Clijsters and then crashing out to the Belgian in the fourth round last year having given up four match points.
Critics of the world number six, and there have been many in China over the years, would point to last year's defeat as an example of the mental fragility that has dogged Li throughout her career.
At times she can be an all-conquering superwoman pounding her opponents into submission with her raking groundstrokes. Just as easily, Li can suddenly fall apart and, apparently unable to string two serves together, plummet to defeat.
There was just a hint of that fragility in her victory over American qualifier Madison Keys at the Sydney International warm-up event on Wednesday, where she lost the first set before reaching the semi-finals with a 4-6 7-6 6-2 victory.
"I was a little bit nervous at the beginning of the match. If you play the young player, you never know what might happen, what they might do on the court," she said after tackling the big-serving teenager for the first time.
"It's very good I could have (a tough) match before Australian Open to see how strong I am on the court though."
Li stood down her coach and husband Jiang Shan after last season and has been working with Justine Henin's former mentor Carlos Rodriguez.
"He gave me a lot of tough times when I was training with him," Li said.
"First three days, my husband didn't come with me. After three days, I was calling him saying, 'Please come with me'. I was thinking about retiring after three days, because he's really, really tough."
The result has been a more attacking Li, even if she is not yet delivering everything Rodriguez wants.
"He feels I can still do even more," she said.
"You know, it's very tough if you've got new thing. You need time to recover. You need time to get used to it. So where once you needed time to think about it, maybe you can do it automatically.
"So now I'm still trying to work like Carlos wants me to."
Li has, however, enjoyed a fine start to the year and, in yet another first, became the inaugural champion at the new Shenzhen tournament last week.
Li was the first Chinese player to win a singles event on the WTA circuit, the first ranked in the top 20 and the first to reach a grand slam quarter-finals, at Wimbledon in 2006.
In 2010, she became the first Chinese player to reach the top 10 and then, in 2011, she reached the Australian Open final before becoming the first player representing an Asian country to win a grand slam singles title at the French Open.
The start of her season has always been strong and she won the title in Sydney in 2011 before reaching the final again last year.
After this week, her rivals know that if Li does melt down in Melbourne, it will not be because of the heat.
Li comes from Wuhan - one of three Chinese cities known as "the furnaces" for their fierce summers - and coolly played through temperatures in excess of 40 degree Celsius in Sydney on Tuesday.
"It felt like playing in a sauna," she said. "But at least I have played in the high temperatures and not gone straight (to Melbourne from China) without any matches inbetween."
2-Angelique Kerber (Germany) beat Svetlana Kuznetsova (Russia) 6-3 7-5
4-Li Na (China) beat Madison Keys (US) 4-6 7-6(2) 6-2
Dominika Cibulkova (Slovakia) beat 3-Sara Errani (Italy) 6-2 6-1
1-Agnieszka Radwanska (Poland) beat Roberta Vinci (Italy) 6-4 7-5
Monica Niculescu (Romania) beat Peng Shuai (China) 3-6 6-4 6-4
Tsvetana Pironkova (Bulgaria) beat 3-Klara Zakopalova (Czech Republic) 3-6 6-4 6-2
Kirsten Flipkens (Belgium) beat Bojana Jovanovski (Serbia) 6-3 6-2
Jarmila Gajdosova (Australia) beat Olga Govortsova (Belarus) 6-3 6-1
- Sports & Recreation