The 31-year-old world No. 4 had previously played in two Australian Open finals and lost both in 2011 and 2013, but those losses came against opponents who were no strangers to the big moment.
In her third appearance in a final in Melbourne, Li came up against a woman in her first Grand Slam final in 24-year-old Slovak Cibulkova.
The 20th-seed had the best fortnight of her career to date making her first final by beating three-time Grand Slam winner and former world No. 1 Maria Sharapova and world No. 5 Pole Agnieszka Radwanska along the way.
It was a tight battle in the first set of the final on Rod Laver Arena with it going to a tie-break, but the Chinese veteran managed to prevail in that and then dominate the second set in just 22 minutes to win the match 7-6 (3), 6-0.
Despite losing the 2011 Australian Open final to Kim Clijsters and then the 2013 final to Victoria Azarenka, Li had already won a Grand Slam title when she beat Italian Francesca Schiavone at Roland Garros in 2011, and now she has two majors to her credit as the first Asian woman to do so.
It was a tight opening to the match with the first set going into a tie-break with both players managing two breaks of serve apiece along the way.
It was Li making most of the play, though, with 22 winners to seven from Cibulkova.
However, 20 unforced errors and six double faults from Cibulkova were uncharacteristic for the Slovak and perhaps highlighted her nerves of playing in a first Grand Slam final.
She did do enough to push Li into a tie-break, though, but while there the 31-year-old showed her experience winning it seven points to three.
Li then took all the momentum out of winning the first set tie-break and she wasn’t about to let her third attempt at winning the Australian Open title slip.
The Chinese star completely dominated the second set not dropping a single game while hitting 10 winners, winning all her break point opportunities, 4-of-6 points at the net and losing just four points on her first serve and only on her second serves.
Cibulkova had put together an outstanding tournament, and played the tennis of her career, but the first set tie-break seemed to take all the steam out of her and she could only win 10 points for the entire second set.