Na Li defeated Serena Williams 0-6 6-1 6-4 in the Stuttgart round of 16 on clay. The upset overturned the form book — Serena Williams came in leading the head-to-head 13–0, defending last year's quarter-final. Na Li claimed a first win over Serena Williams in 14 meetings, narrowing the head-to-head to 13–1.
| Date | Tournament | Round | Surface | Winner | Score |
|---|---|---|---|---|---|
| 2014-03-17 | Miami | F | hard | Serena Williams | 7-5 6-1 |
| 2013-10-27 | Istanbul | F | clay | Serena Williams | 2-6 6-3 6-0 |
| 2013-10-21 | WTA Championships | F | hard | Serena Williams | 2-6 6-3 6-0 |
| 2013-08-26 | US Open | SF | hard | Serena Williams | 6-0 6-3 |
| 2013-08-17 | Cincinnati | SF | hard | Serena Williams | 7-5 7-5 |
| 2013-03-18 | Miami | QF | hard | Serena Williams | 6-3 7-6 |
| 2012-10-24 | Istanbul | RR | clay | Serena Williams | 7-6(2) 6-3 |
| 2012-10-22 | WTA Championships | RR | hard | Serena Williams | 7-6 6-3 |
| 2010-06-21 | Wimbledon | QF | grass | Serena Williams | 7-5 6-3 |
| 2010-01-18 | Australian Open | SF | hard | Serena Williams | 7-6 7-6 |
| 2009-07-27 | Stanford | R32 | hard | Serena Williams | 6-3 7-6 |
| 2009-03-23 | Miami | QF | hard | Serena Williams | 4-6 7-6 6-2 |
| 2006-01-16 | Australian Open | R128 | hard | Serena Williams | 6-3 6-7 6-2 |
Averages over each player's completed matches in the selected window (200 vs 198). ATP, WTA & Challenger.
Performance in the biggest moments — break points, deciding sets and tiebreaks (0–100, higher is better). About
Each player's serve crossed against the other's return, converted to expected hold of serve. Recent completed matches, ATP, WTA & Challenger. About