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The 12th seeded Serb, who made the Wimbledon semi-finals in 2007, was beaten 6-3, 6-3 in 63 minutes by the 19-year-old Bouchard, who is making her main draw debut at the All England Club.
Bouchard, the world number 66, faces Spanish 19th seed Carla Suarez Navarro in the third round.
The match was swiftly rescheduled for Centre Court after second seed Victoria Azarenka withdrew from the tournament just before her match against Flavia Pennetta, citing the nasty right knee injury she sustained during her first round match.
"We found out 15 minutes before going on court so I was really excited, it was crazy and great to play before this crowd," Bouchard said.
On speculation that she could be the next big thing in women's tennis, she said: "It's nice to hear those things for sure. I'm really happy to play well again here. Last year I won the juniors so it feels like my second home here, I love it here."
Meanwhile, Lleyton Hewitt was also dumped out of Wimbledon on Wednesday by German qualifier Dustin Brown, the dreadlocked former Jamaica player ending the 2002 champion's hopes of an impressive comeback run.
Brown, whose fluid style and range of shots won him fans on Court 2, beat the Australian veteran 6-4, 6-4, 6-7 (3/7), 6-2 in the second round clash.
Hewitt, the world number 70, has defied the surgeons to continue his career after two years blighted by injury and operations, had been looking to make an impact at the All England Club where he triumphed 11 years ago.
Back in form, he got to the Eastbourne warm-up tournament semi-finals and knocked out Swiss 11th seed Stanislas Wawrinka in the first round.
Brown, 28, the world number 189, changed nationality from Jamaican to German in 2010. He was born in Germany to a Jamaican father and German mother. He moved to Jamaica aged 12.
The win takes him through to a first Grand Slam third round match.
"It's going to take a while to sink in. I'm not normally the type of guy to cry," he said.
He next plays world number 111 Adrian Mannarino.
The Frenchman made it through when US 18th seed John Isner pulled out two games into their second round match after injuring his knee.
