The Briton was featuring in the main draw for the first time and was up against the player, ranked 31 places below her, who she lost to in the Wimbledon first round after being a set up.
The Scot said it was a "good chance to get revenge" and she did not disappoint, producing an effortless display on a sweltering opening day on court 17.
Two breaks in a first set that included no double faults or unforced errors would have settled any early nerves, and she eased through the second set in 35 minutes to banish any lasting memories of her defeat in London in June.
"Losing to her at Wimbledon was very difficult to take, because I was two points away from the match," Baltacha added. "I thought I had that one in the bag and then all of a sudden I was 5-3 down in the third set and I couldn't believe it.
"I took that loss quite hard and there were a lot of things to get over after that match but it was one of those things that would make me or break me.
"I always try to think things happen for a reason, however hurtful, and after Wimbledon really tested me mentally and emotionally. There were a couple of demons there and after today I think I've flicked the demons off my shoulder.
"I learned a lot of things from from that match and it helped a lot [on Monday]. I knew it was going to be one of those interesting matches but I knew that if I stayed very professional and focused in hard and try to deliver my best tennis then I knew that I could win.
Baltacha will face Kvitova for a place in the third round after the Czech Republic star beat her compatriot Lucie Hradecka 6-4 7-5.
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