Williams is returning to the grass-court tournament for the first time since 2016 after missing it last year while pregnant. She gave birth to a daughter in September.
She is ranked outside the top 150, but the All England Club decided to seed her 25th based on past success, which includes collecting seven of her 23 Grand Slam singles trophies at Wimbledon. Williams' first-round opponent when play begins Monday will be 107th-ranked Arantxa Rus of the Netherlands, who has one career tour title.
Williams is competing for the first time since she pulled out of the French Open ahead of a fourth-round showdown against five-time major champion Maria Sharapova in early June, citing an injured chest muscle. That was Williams' return to Grand Slam action after a 16-month absence.
Rus has only once been as far as Wimbledon's third round, back in 2012. That was the last time she won a match at the All England Club. She was beaten in the first round of qualifying a year ago, as were both of the women Williams could meet in the second round, 136th-ranked qualifier Viktoriya Tomova of Bulgaria and 167th-ranked wild-card recipient Tereza Smitkova of the Czech Republic.
Svitolina has only once been as far as the fourth round.
Williams' possible fourth-round opponent, 2017 US Open runner-up Madison Keys, has made one quarterfinal appearance, while the 36-year-old American's potential quarterfinal foe, reigning Australian Open champion Caroline Wozniacki, has never been beyond the fourth round.
In the top half of the women's bracket, the quarterfinals could be French Open champion Simona Halep vs. two-time Wimbledon winner Petra Kvitova, and defending champ Garbine Muguruza vs. No. 6 Caroline Garcia. In the bottom half, No. 2 Wozniacki was drawn to face Svitolina, while 2017 US Open champion Sloane Stephens could play No. 7 Karolina Pliskova.
The potential men's quarterfinals in the top half are eight-time champion Roger Federer vs. 2017 US Open runner-up Kevin Anderson, and 2014 US Open champion Marin Cilic vs. No. 6 seed Grigor Dimitrov. In the bottom half of the bracket, it could be two-time Wimbledon winner Rafael Nadal vs. 2009 US Open champion Juan Martin del Potro, and No. 4 Alexander Zverev vs. No. 7 Dominic Thiem.
That was Murray's last win before he sat out nearly a year because of an injured hip that was surgically repaired in January.
He returned to action last week, so is ranked only 156th and unseeded at Wimbledon, which he won in 2013 and 2016.
Murray could face 26th-seeded Denis Shapovalov of Canada in the second round.