Top seed Djokovic, looking to equal Pete Sampras as a seven-time champion at the All England Club, downed his 104th-ranked opponent 6-2, 4-6, 6-1, 6-2.
The Serb will face 10th seeded Jannik Sinner for a place in the semi-finals after the Italian knocked out Spanish teenager Carlos Alcaraz.
"He was very tough. I have never faced him before," said Djokovic after racking up a 25th successive win on grass.
"He has a great serve, powerful forehand and nice touch."
Djokovic cruised through the opening set under the Centre Court roof with breaks in the second and eighth games.
However, Van Rijthoven stunned the 20-time Grand Slam title winner by levelling the contest, pocketing the second set with his 13th ace of the tie.
Normal service was resumed, however, in a 30-minute third set on the back of a double break for the champion.
Two further breaks against the wilting Dutchman, who ended the contest with 53 unforced errors, proved enough for Djokovic in the fourth set.