The native of Westmount, Que., who made headlines in Canada last week after unexpectedly making the final four in Melbourne, will be joined by Gabriela Dabrowski of Ottawa, Sharon Fichman of Toronto and Aleksandra Wozniak, Blainville, Que.
The World Group II first-round series will be played indoors Feb. 8-9 at the Claude-Robillard Sports Complex.
"The team that will defend Canada's colours consists of experienced players on the international scene," said Canadian captain Sylvain Bruneau. "The girls are ready to take on the tough challenge that awaits them against Serbia and move one step closer to the World Group."
The best-of-five series will mark Bouchard's return home after her stellar Australian Open performance, which moved her up to No. 19 in the world rankings. The 19-year-old made her Fed Cup debut in 2011 and has a record 7-2. Last year in Kyiv, Bouchard won two matches despite playing with an injured ankle, including the decisive doubles with Fichman to give Canada a place in World Group II for the first time since 2010.
Dabrowski, the country's top doubles player at No. 61 on the WTA rankings, 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. She's 3-0 in Fed Cup play.
Fichman enjoyed the best season of her career in 2013, making the world's top 100 for the first time (95th). In her first tournament of 2014 at Auckland, Fichman collected her first WTA doubles title. In Fed Cup, Fichman is 22-7 since making her debut in 2005 at the age of 14.
Wozniak has struggled with injuries and will be playing her first Fed Cup tie since 2011. A member of the Canadian squad since 2004, she holds a 37-9 record on the circuit.
Canada lost 3-2 to Serbia in 2011.