Second seed Karolina Pliskova and rising stars Stefanos Tsitsipas and Denis Shapovalov also have their sights set on advancing.
>ORDER OF PLAY: Day 5 – Thursday October 1
Following a first-round scare Pliskova will need to be on her game when she meets Latvian 2017 Roland-Garros champion Ostapenko first up on Court Philippe-Chatrier.
The winner of this year's Australian Open, Kenin follows when she takes on Romanian Ana Bogdan.
Roland-Garros 2016 champion Djokovic continues his bid for Grand Slam title No.18 when he faces Lithuanian Ricardas Berankis before fifth seed Tsitsipas will attempt to back up from his five-set first-round win against Uruguay's Pablo Cuevas.