While most of the world's best players are taking a break following two weeks of gruelling competition at the All England Club, Williams has jumped straight back into the fray.
She was given a very gentle test against a Belgian qualifier ranked outside the top 200, however, and completed a 6-2, 6-1 victory in quick time to advance to the second round.
"I had never played her before so I didn't know what to expect," Williams said. "And she had a really big serve and some really good holds – she played really well. It definitely wasn't an easy match."
Williams was pleased with her performance on her return to clay following the conclusion of the grass court season.
"It's just so much easier to go from grass to clay than from clay to grass," she said.
"It's really not bad. I'm getting used to it. It's worse the other way around!"
Williams next faces a tricker opponent in Klara Koukalova, who has a victory against her on clay.
"She's beaten me before. I played her once at the French Open too, we had a long three set match – it was actually a two day match," Williams added. "She's never fun to play, so it'll be a good match."
In the day's only other first-round match, seventh seed Johanna Larsson beat Richel Hogenkamp 6-1, 6-3.
In second-round action which got under way on Wednesday, second seed Samantha Stosur was eliminated by Lara Arruabarrena, who fought back from 2-4 down in the first set to complete a 7-6 (7-5) 6-0 victory.
Jana Cepelova and Mona Barthel also advanced to the quarter-finals, Cepelova beating Olga Govortsova 4-6, 6-3, 6-2 and Barthel thrashing Maryna Zanevska 6-0, 6-0.