At a pre-match ceremony Friday in front of photographers, Romania's Alexandra Dulgheru stuck out her hand but was rebuffed with a dismissive wave.
"No, I'll pass," Bouchard said.
It was an awkward moment taken in stride by the No. 66-ranked Dulgheru, who smiled and crossed her arms.
Dulgheru got her revenge on the court Saturday, beating Bouchard 6-4, 6-4 in their singles match.
Bouchard said earlier that she was just engaging in gamesmanship.
"It's nothing personal towards her, I just don't believe in wishing my opponent good luck before the match," Bouchard told Romanian media. "After we play [Saturday] I will shake her hand, no matter what happens."
This isn't the first time Bouchard has refused a handshake. Last year, at another Fed Cup World Group pre-match ceremony, she gave the cold shoulder to Kristina Kucova of Slovakia in a similarly awkward moment.
Canada and Romania are meeting over the weekend for five rounds of competition featuring four women's singles matches and a women's doubles match. The winning nation will qualify for the 2016 Fed Cup World Group.