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The 25-year-old, who will make his second appearance at the ATP Finals, defeated Australia's Alexei Popyrin 7-6(3), 6-3 in the opening round of the Vienna Open.
Alcaraz became the youngest male player to reach the fourth round of a Grand Slam since 17-year-old Andrei Medvedev at 1992 Roland Garros.
American Frances Tiafoe caused the first big upset by beating third seed Stefanos Tsitsipas 6-4, 6-4, 6-3.
The Serbian world No. 1 increased his Grand Slam tally to 19 titles, and is now one adrift of the men's record held by Roger Federer and Rafael Nadal.
Djokovic came from a set down in a spellbinding semifinal to inflict only a third ever defeat on the Parisian clay for Nadal.
The Greek got revenge for his Australian Open semifinal loss to the Russian this year and improved his Grand Slam quarterfinal record to 4-0 with a 6-3, 7-6(3), 7-5 win that teed up a last-four clash against Germany's Alexander Zverev.
Nadal improved his unbeaten record to 12-0 in finals at one of his favourite ATP events where the main showcourt carries his name.
Nadal's bid for a record 21st Grand Slam title ended with a quarterfinal defeat to the Greek.
The Greek teenager, who turns 20 on Sunday, followed up his defeat of seventh seed Dominic Thiem, beating four-time champion Djokovic, seeded ninth, in a first-time meeting.
With professional tennis unlikely to return before early August, at the earliest, Tsitsipas says the hardest thing has been training without an end goal.
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