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Riddler's Frogmen were men working for the Riddler.
During Batman and Robin's assault on the Riddler's fortress, Claw Island, Two-Face managed to destroy the Batboat piloted by Robin by setting off one of the Riddler's underwater mines, although Robin escaped death by ejecting himself from the Batboat just mere seconds before it's destruction. Robin then attempted to swim towards Claw Island when he was attacked and overpowered by the Riddler's Frogmen, who removed his underwater breathing device and tried to drown him. Batman, whose Batwing was blasted and destroyed by the Riddler himself, saved Robin by trapping the Riddler's Frogmen in a net.