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I know Batman's lost one-on-one to Kobra, Deathstroke, and Prometheus. There are quite a few villains who have beaten Batman in their first encounter, particularly martial artist-types; I'm pretty sure Lady Shiva and Richard Dragon both beat him their first time out, as well as Bronze Tiger, and Karate Kid from the Legion of Super-Heroes has been able to beat him before too.
Oh, and one time Superman beat him nearly to death when Max Lord made him hallucinate that Batman was Darkseid (and was only stopped by Wonder Woman, so that makes her 2 for 2 against both of DC's favorite sons).
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