Wozniak and fellow Canadians Eugenie Bouchard and Stephanie Dubois are the three wild-card entrants in the main draw of the women's tournament which was held downtown in Place du Canada on Monday.
Top-ranked Victoria Azarenka of Belarus, the tournament's first seed, won the first Olympic gold medal in mixed doubles since 1924 on Sunday at Wimbledon.
She and partner Max Mirnyi defeated Olympic men's singles champion Andy Murray and Laura Robson of Great Britain 2-6, 6-3, 10-8.
Olympic gold medallist Serena Williams and her sister, Venus, will not be in Montreal, though the rest of the top-ranked women will be taking part, including Agnieska Radwanska of Poland, Russia's Maria Sharapova and Australian Samantha Stosur, who lost the 2011 Rogers Cup final in Toronto to Serena Williams.
Petra Kvitova, Angelique Kerber, 2010 Rogers Cup champion Caroline Wozniacki, Marion Bartoli and Li Na round out the top 10 seeds.
"All the girls that were there at the Olympics are here, other than just a few like Serena," said Wozniak, a native of Blainville, Que., who was ranked a career-high 21st in the world in 2009.
"They love this tournament. I think it's great for the fans that come out and support all of the tennis players."
Play in the main draw gets underway Tuesday with the top 16 seeds enjoying a first-round bye.
Currently ranked 52nd, Wozniak lost her second-round match at the Olympics to Serena Williams, who defeated Sharapova in the final to win her first Olympic singles gold medal.
"I'm healthy and I'm treasuring it as much as I can," Wozniak said. "My preparation is going well. It's a question of adapting from changing surface from grass to hard court, and also the time change."
She is looking forward to taking centre stage at home.
"You feel the energy," Wozniak said. "It's different when you step out on the centre court and it kind of helps you surpass your limits when you feel that crowd."
Bouchard, who is ranked 237th in the world, will face Israel's Shahar Peer in the first round.
"I hope there are lots of people to come support me," Bouchard said. "I love the home crowd advantage. We don't get it all the time, travelling around the world, we rarely get it, so I always try to use it to my advantage."
Odds are that Bouchard will receive a hero's welcome when she faces Peer.
The 18-year-old native of Westmount, Que., became the first Canadian to win an individual Grand Slam title on July 7 when she beat Ukraine's Elina Svitolina in straight sets to win the junior girls' final at Wimbledon.
"The biggest crowd was in Wimbledon," said Bouchard, who also partnered with American Taylor Townsend to win her second straight junior girls' doubles title at Wimbledon. "There were like 8,000 people for the final there so that was the biggest one. I'm used to it, I think."
Dubois, a Laval, Que., native who is ranked 151st, will face South Africa's Chanelle Scheepers in her first-round match.