At the site of nuclear accidents, firefighters situated near nuclear power plants (NPPs) assume responsibility for suppressing fires and rescuing workers from leaked radiation. Their timely responses to nuclear emergencies can prevent or minimize the catastrophic impacts of these accidents. Despite their important role in nuclear emergency management, little is known about the factors that influence firefighters’ nuclear emergency responses. We recruited 179 Korean firefighters (96% male) situated near NPPs. We examined whether and how knowledge regarding nuclear accidents and trust in the authorities operating nuclear power plants were related to firefighters’ risk perceptions of nuclear accidents to predict their preparedness and willingness to respond to nuclear emergencies. Our results indicate that trust moderated the effect of knowledge on the perceived risk of nuclear accidents, and that the perceived risk mediated the relationship between knowledge and firefighters’ preparedness and willingness to respond to nuclear emergencies. The results revealed a pattern of moderated mediation, in which perceived risk mediated the indirect effect of knowledge on preparedness and willingness when the firefighters’ trust was low, but not when it was high.