Bouchard, who grabbed the tennis world's attention at last month's Grand Slam, will be joined in the best-of-five series by Gabriela Dabrowski of Ottawa, Sharon Fichman of Toronto and Aleksandra Wozniak, of Blainville, Que.
The 19-year-old rising tennis star said Wednesday she took time off after the Australian Open, and only worked a little bit on her serve and a few technical issues.
"I was definitely physically and mentally tired," Bouchard told a news conference at Montreal's Claude-Robillard Sports Complex, the site of Saturday and Sunday's indoor World Group II first-round series women's tie.
"I'm happy with what I did, but never satisfied. I wanted to do better. At the end of the day I lost in the semifinals, so ... I hit the practice court and I'm going to continue to work hard on court to try and do better."
Bouchard, whose success in Melbourne moved her up to No. 19 in the world rankings, made her Fed Cup debut in 2011 and has a record of 7-2.
Last year in Kyiv, Bouchard battled an injured ankle and won two matches, including the decisive doubles match alongside Fichman. That victory gave Canada a place in World Group II for the first time since 2010.
Dabrowski, the country's top-ranked female doubles player at No. 61 in the WTA computer, reached her first two WTA doubles finals in 2013 at Brussels and Linz in addition to winning two doubles titles of the ITF Challenger Circuit. The 26-year-old is 3-0 in Fed Cup play.
The 23-year-old Fichman has a 22-7 career record at the Fed Cup, while Wozniak, 26, is 37-9.
The Canadians will square off this weekend with a young, less-experienced Serbian team that will be missing two of its top players: Jelena Jankovic and Ana Ivanovic, a former world No. 1.
Bouchard, who upset Ivanovic in the quarterfinal at the Australian Open, said Wednesday her team would have liked to meet them in the Fed Cup.
"I think we're all disappointed not to have the two best, Ivanovic and Jankovic, here," said Bouchard.
"But now we will take advantage, we will try to do our best and I think we have all the best players in Canada here. They might not have their best, so we will use that to our advantage."
Serbian team captain Dejan Vranes said Ivanovic won't play this weekend due to injury and that Jankovic no longer competes in the event.
The country will be represented by Nina Stojanovic, 17, Aleksandra Krunic, 20, Jovana Jaksic, 20, and Vesna Dolonc, 24, who at No. 117 is its top-ranked player.
Vranes called the Canadians the favourites, particularly since they will be playing in front of a home crowd in a venue that holds some 4,000 fans.
"We have a great challenge in front of us, but I believe in our team and I think we have a chance in every match," a confident Vranes told reporters.
"We'll be ready to fight."
The Canadian women, however, are aiming to continue Canada's recent stretch of strong tennis performances.
On the men's side, Milos Raonic climbed into the top 10 in the world last year, while Vasek Pospisil also rose in the rankings. Both reached the Rogers Cup semifinals in Montreal last summer and led the Davis Cup team to a first-ever semifinal appearance.
Wozniak said she hopes the women can also deliver their own record-breaking finish.
"We're looking forward to the challenge, and what the men did, it's made history in Canada," Wozniak said.
"So, I think for me, and for the team, it's important. We would love to make a new history for Canada and win this tie."
For Bouchard, who grew up in the Montreal Island community of Westmount, there's the bonus of playing a match in her hometown for the first time in a year and a half.
"It's always fun to play in Montreal," said Bouchard, who was asked whether more people seem to recognize her in the city since the Australian Open.
"Yeah, for sure, there are people who say, 'Good luck' and that they are proud of me. It's special. I'm happy to get compliments like that."