Duan, who had never won a main draw match at a Grand Slam - she was 0-4 - looked a little bit out of sorts early on, as Bouchard went out to a 2-0 lead. But the big-hitting Chinese quickly got herself back into it, breaking back, and after 48 minutes and a slew of set points she had the set in a tie-break.
The second set was dead even through the first eight games as neither player would budge on serve, but Duan snuck out one last critical break at 4-all then served out a 7-6(3), 6-4 victory on Court 3.
Duan's win over the World No.12 on Tuesday was the first Top 20 of her career.
"I definitely felt tight in the first set. But I also felt very unprepared for this match. That's unfortunate. But I wanted to play, no matter what," Bouchard said. "After Eastbourne we did testing and I have a grade two tear in my ab. It probably wasn't smart to play here, but I couldn't pass on Wimbledon.
"So I did kind of minimal preparation to save myself for this match."
And how did it feel on the court? "I mean, it was taped, and it felt okay, but I was just trying not to think about it. But I just haven't practiced that much. So I felt that my timing was very off out there.
"It's unfortunate that this happened at my favorite tournament of the year, and that I won't get to play any more matches here this year, but I'm going to try to put it behind me and just look forward."
Bouchard, who went as high as No.5 in the world last year, is hoping for some rest and recovery now.
"I'm going to take some time to heal and maybe not think about tennis for a little bit," she said.
"And then I'll get right back to it."
The Canadian is projected to fall out of the Top 20 on the WTA Rankings after this first round loss but with little to defend the rest of the year, could we see a resurgence in the second half of 2015?