Second seed Rafael Nadal will play Argentina's world number 42 Francisco Cerundolo in the first round while young sensation Carlos Alcaraz will take on Germany's Jan-Lennard Struff.
She won the last of her seven Wimbledon singles titles in 2016 but reached the final in 2018 and 2019 after returning to the court after having a baby.
The defending champion is the top seed after the Russian world number one Daniil Medvedev got banned from taking part while German world number two Alexander Zverev is out due to injury.
The 18-year-old American, who reached her first Grand Slam final at the Roland Garros earlier this month, registered a 7-5, 6-4 win over fourth seed Pliskova in just one hour and 37 minutes.