The 28-year-old Canadian has struggled with injuries and form since being defeated by Petra Kvitova in the 2014 final, and has dropped to 218th in the world as a result.
Bouchard has not progressed beyond the quarter-finals in any tournament since March 2021 and suffered more disappointment at the hands of Belgian Greet Minnen, the world number 120, in her opening match at Roehampton, losing 6-4 7-5.
Another former finalist from 2010, Vera Zvonareva, fared better with a three-set victory over Brazil's Laura Pigossi in almost three hours.
The 16-year-old Mirra Andreeva, who reached the third round at the French Open, progressed with a straightforward 6-3 6-1 win over Spaniard Rosa Vicens Mas.
Britons Naiktha Bains and Yuriko Miyazaki both progressed to the next round with victories over Ukraine's Katarina Zavatska and South Korea's Han Na-lae respectively.
Hannah Klugman, aged 14, and 15-year-old Mingge Xu's first experiences of qualifying ended in defeat, the former losing 6-1 7-6 (6) to Reka Luca Jani, at 31 more than twice her age, and Xu going down 7-5 6-4 to Australia's Storm Hunter.
Players need to win three matches to secure a place in the main draw.
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