She will face off for the title against world number two Victoria Azarenka, who won a match plagued by breaks of serve -- 23 in total, including the first six games -- to defeat 2011 finalist Jelena Jankovic 4-6, 6-2, 6-3.
Azarenka and Williams will both be playing for their first title at the tournament. Azarenka finally earned her victory with a concluding break of former number one Jankovic.
World number one Williams, who has won 15 titles in the last 16 months and is bidding for her ninth this season, needed just over 90 minutes to advance against the error-prone 2012 winner here.
Li ended in unfortunate fashion, double-faulting on a set point in the first and again on match point in the second. Williams claimed her eighth win in nine matches against Li, who had not played in the previous round when opponent Agnieszka Radwanska withdrew to attend a funeral in her native Poland.
China's former Roland Garros winner had a bad day on serve, double-faulting on a set point in the first set and ending the contest after 83 minutes with the same costly error on match point.
Williams' previous best in Cincinnati was a semi-final in 2006 when it was a smaller women's-only tournament. "When you win a lot you develop a lot of confidence and a belief that you can do well," said the 31-year-old. "I've been training more and enjoying it a lot over the past year and a half."
Williams also won the US Open Series title which gives her a chance at a one million-dollar bonus should she win the US Open which begins a week from Monday. The American admitted to dealing with an abdominal muscle problem this week but did not go into details, saying she did not want to tape it for fear it might hinder her movement.
The top seed went up 4-1 in the first set only to be pegged back by Li, who then served for the match but failed. Williams levelled at 5-5 on another of Li's eight serving errors and then broke again to win the set after 47 minutes.
The American then trailed in the second but with Li again unable to serve out. The top Chinese finally went down to defeat after losing serve seven times. The win earned Williams a 60-3 record this season.
Nadal to meet Isner in Cincinnati final
Meanwhile, Rafa Nadal continued his perfect run on the North American hardcourts taming Czech Tomas Berdych 7-5 7-6 (4) at the Western and Southern Open on Saturday to setup a final showdown with big-hitting American John Isner.
Earlier, unseeded Isner had blasted his way into the final with a 6-7 (5) 7-6 (9) 6-3 marathon win over Argentine Juan Martin Del Potro.
Rebounding nicely from a shock first round upset at Wimbledon, Nadal has been in sizzling form picking up his 58th career title last week in Montreal while extending his hardcourt winning streak to 14-0 with a run to the final in Cincinnati.
A win on Sunday in his first Cincinnati final would give the third ranked Spaniard his ninth title of the year and leave him the red-hot favourite heading into the U.S. Open which begins on Aug. 26 in Flushing Meadows.
Additional reporting by Reuters and SAPA-AFP
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