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Alcaraz became the first man to defend a championship in the California desert since Novak Djokovic won three straight between 2014 and 2016.
Alcaraz came from behind to beat Jannik Sinner before Medvedev edged out American Tommy Paul 1-6, 7-6(3), 6-2 in the second semifinal.
Third seed Coco Gauff served up 17 double faults but still managed to beat China's Yuan Yue 6-4, 6-3 to reach the women's semifinals in the Californian desert for the first time.
Humbert became only the third player in the professional era to win his first six tour-level finals, matching the achievement of Latvia's Ernests Gulbis and Slovakia's Martin Klizan.
A Russian-speaking official appeared to accuse him of using an obscenity, while he screamed at the line judge.
Carlos Alcaraz, Jannik Sinner, Daniil Medvedev and Holger Rune will also play at the 'Six Kings Slam', which will form part of the Saudi cultural and entertainment festival Riyadh Season.
The 22-year-old fourth seed is the first Italian to win the Melbourne Park title.
Sinner broke for a 3-1 lead in the fourth set and ran away with the match to snap the Serb's 33-match winning run at Melbourne Park and end his quest for a record 25th major.
The German stunned second seed Alcaraz 6-1 6-3 6-7(2) 6-4 in the quarterfinals.
Yastremska, the world No. 93 who reached the third round at Melbourne Park in 2019, secured the early break in the second set as her opponent continued to spray the errors and the 23-year-old held firm to seal the victory.