There were constant reminders of her opponent's greatness at every turn.
Framed photos of Williams in her championship glory hang throughout the venue. Large banners documenting her five Wimbledon singles titles are also on display at the All England Club.
Williams used the dominating style she's known for early against the Canadian and never let up, powering past Wozniak 6-1, 6-3 in just over an hour.
"My arm was on fire returning her serves," Wozniak said. "They were so huge."
Wozniak appeared to have some early jitters in her first career appearance on the historic court.
She opened with a double fault and Williams crushed her next serve for a forehand winner. Williams secured an early break and was on her way to a comfortable win.
"It feels like it's really her tournament," Wozniak said. "I feel like she's unbeatable here. The way she played today, I don't think she could have played any better.
"You can really sense that the Centre Court is hers."
Williams won her most recent tournament title 2 1/2 years ago, and she took a long layoff after being diagnosed in 2011 with an autoimmune disease that causes fatigue.
At age 32, she seems rejuvenated by the chance at a record fourth gold medal in Olympic tennis.
"Every day I'm just concentrating on trying to bring my best tennis out," Williams said. "And honestly, if there's a time to do it, it's now."
Her world ranking has plummeted to No. 72 but she has looked strong in both matches so far.
Wozniak, the world No. 52 from Blainville, Que., has never made it past the second round at Wimbledon and has one career WTA tournament win. However, she has pushed Williams to the limit in the past, taking her to a third-set tiebreaker last March in a loss at Miami.
Sylvain Bruneau, a travelling coach who has served as Canada's Fed Cup captain, said Williams looked comfortable throughout the match.
"It's like her house, that court," he said. "She's won (Wimbledon) five times and she's played there so many times. It's a little bit of an advantage but that's the way it goes."
Wozniak, who beat Marina Erakovic of New Zealand 6-2, 6-1 in the first round, was in decent spirits afterwards. The 24-year-old was grateful that her Olympic debut could be made at the storied club.
"The tradition and everything, it gets to you," she said. "All the legends who have been here. I was really happy to be a part of this and represent my country at the Olympics."
Wozniak has had to share the Canadian tennis spotlight of late with Milos Raonic of Thornhill, Ont., who has risen to No. 25 in the men's rankings.
Raonic has posted some big wins since his breakthrough season last year. Wozniak is happy for his success and doesn't mind that he has been making more headlines.
"I think in Quebec everyone they know me and in Canada now he's made a place for himself too," she said. "He's working really hard and he represents the country."
"They haven't forgotten me," she added with a laugh.
The Canadian players are staying at a house near the club this week since the Olympic Village is on the other side of town. Wozniak said she's enjoying the camaraderie with her Canadian teammates.
"It's nice to have the support," she said. "Everyone hanging out together, it's nice."
Williams has won five of her seven major titles at the All England Club, most recently in 2008. Her opponent Wednesday will be No. 7 Angelique Kerber of Germany, who beat Timea Babos of Hungary 6-1, 6-1.
Against Wozniak, Williams took charge by winning eight consecutive games — which she didn't realize.
"I know I'm in the zone when I don't know the scores," she said. "In the second set, I had to look up and see what the score was. I didn't realize the first set was 6-1. I'm just playing. So that's always a good sign."
A four-time Olympian, Williams won the gold in singles at the 2000 Games and teamed with Serena to take the gold in doubles in 2000 and 2008. They are also entered as a doubles team in London.
With files from The Associated Press.