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The third seed, Zverev produced 15 winners and nine unforced errors, compared to 12 and 25, respectively, for Humbert.
Taylor Fritz toppled Alexander Zverev with a 4-6 6-7(4) 6-4 7-6(3) 6-3 victory to reach the quarterfinals.
Kazakh Yulia Putintseva who battled back superbly won the third-round clash 3-6 6-1 6-2 against Swiatek.
Vondrousova became the first female holder to fall at the opening hurdle since Steffi Graf 30 years ago.
The 21-year-old also became the seventh man and the youngest to capture Grand Slam titles on all three surfaces.
Carlos Alcaraz reached his maiden French Open final with a 2-6 6-3 3-6 6-4 6-3 win over Jannik Sinner before Alexander Zverev also recovered from a slow start on Friday to beat Casper Ruud.
The agreement, according to German media, includes a monetary condition of 200,000 euros ($217,820), with the player not found guilty of any wrongdoing.
Zverev edged Dutchman Tallon Griekspoor 3-6 6-4 6-2 4-6 7-6 (10-3).
The Spaniard, who turns 38 next month, lost 6-3, 7-6 (7/5), 6-3 to Alexander Zverev.
Novak Djokovic will begin his quest for a 25th Grand Slam crown against local hope Pierre-Hugues Herbert, while top-ranked Iga Swiatek kicks off her title defence against a qualifier.
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