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Serena had to rally back from a set down and 4-2 final set deficit to prevail in a thrilling battle.
There was a brief loss of focus when Djokovic was broken to love midway though the second set but he was quickly back in the groove to move two sets ahead.
Ashleigh Barty overwhelmed British wild card Harriet Dart 6-1, 6-1.
While the women's game is often exalted as being wildly unpredictable, Williams remains the exception to the rule and Tuesday's win secured her a 37th Grand Slam semi-final appearance.
Williams, who faces fellow American Alison Riske in the quarter-finals on Tuesday as she looks to win her 24th Grand Slam title, has yet to comment on the fine.
The 37-year-old will become the oldest woman to contest a Grand Slam final in the professional era.
Serena, who first played at the All-England club as a 16-year-old in 1998, said she was still ambitious.
A day when Serena had been expected to equal Margaret Court's all-time record of winning 24 Grand Slam singles titles ended with the 37-year-old American suffering her heaviest defeat in a major final at the hanads of Simona Halep.
The result denied Serena Williams from equalling Margaret Court's all-time record of winning 24 Grand Slam singles titles.
The former world No. 1 was knocked out of the French Open in the third round following a 6-2, 7-5 defeat by fellow American Sofia Kenin.
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