Long before Harley Quinn hit the scene in DC Comics, the Joker had another second in command who discovered Batman's secret identity. Black Queen was a fitting second in command for Joker, and worked out Bruce's secret through pure deduction.
While Harley Quinn discovered Batman’s secret identity long after the Joker involuntarily learned the truth, DC’s first Harley Quinn found out Batman was actually Bruce Wayne decades before either of them–and did so after her first time meeting the Caped Crusader.
Harleen Quinzel became the infamous Harley Quinn after she was seduced by the Joker in Arkham Asylum while acting as his psychiatrist and joined him on his crusade of senseless villainy and unparalleled violence. After going off on her own and cutting all ties with the Joker, Harley Quinn became something of an antihero and is currently on the road to full-blown heroism as she has time and again assisted Batman on his missions.
Upon boarding the ship, the Joker tasks the Black Queen with eyeballing some of the best targets, which, of course, included known billionaire Bruce Wayne. When the Black Queen gets close to Bruce in an effort to seduce and eventually rob him, she notices a tiny cut on his chin, though she doesn’t think anything of it. However, when Batman shows up later to stop the villains, the Black Queen notices the same cut on his chin and figures out then and there that Batman is actually Bruce Wayne.
Harley Quinn knows who Batman is in Batman: White Knight as the two end up working closely together. The Joker, on the other hand, has never made it clear when he first found out, but makes a show of not wanting to know in the series Death of the Family where Batman tries to tell him his name and the Joker just won’t hear it as he doesn’t want to be reminded that Batman is just a man under his cowl.
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