Williams took her fourth Wimbledon title last year but was forced to stay away from tennis since then after undergoing foot surgery and then developing blood clots in her lung. She finally announced coming back for the grass-court Grand Slam and warmed up at Eastbourne earlier this month.
Fifth seed Maria Sharapova, the 2004 champion, powered past Russian Anna Chakvetadze 6-2, 6-1 and next faces either British wildcard Laura Robson or Germany's Angelique Kerber.
Women's world No. 1 Caroline Wozniacki raced into the second round as she routed Spain's Arantxa Parra Santonja 6-2, 6-1, taking just 59 minutes to demolish the world number 105.
Former world number one Jelena Jankovic, the 15th seed, went out to Spanish left-hander Maria Jose Martinez 5-7, 6-4, 6-3.
Fourth seeded Belarusian Victoria Azarenka went through when Magdelana Rybarikova of Slovakia retired with a knee injury in the second set.
Czech eighth seed Petra Kvitova, a semi-finalist in 2010, stormed past American qualifier Alexa Glatch 6-2, 6-2.
In the men's singles, the seeds also enjoyed a flying start. Six-time men's champion Federer, chasing Pete Sampras's record of seven titles, cruised to a 7-6 (7/2), 6-4, 6-2 win over Mikhail Kukushkin of Kazakhstan. The third seed will next face France's Adrian Mannarino.
Second seed Djokovic, playing for the first time since Federer ended his 43-match winning run in the French Open semifinals, was equally untroubled needing just 80 minutes to defeat France's Jeremy Chardy 6-4, 6-1, 6-1.
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