Response habituation is a fundamental form of nonassociative learning, yet there are substantial individual differences in its electrodermal manifestation. We employed a latent class analysis to identify discrete groups of electrodermal responders to a series of loud tones. We also evaluated whether heterogeneity in responsiveness was associated with lifetime prevalence of externalizing psychopathology and major depression. Participants were community‐recruited men (N = 1,141) who underwent a standard habituation paradigm. A latent class analysis resulted in the identification of four electrodermal populations: rapid habituators, habituators, and two classes that showed weak response habituation, but differed markedly in their amplitude profiles. Relative to rapid habituators, members of slower habituating classes were less likely to receive lifetime diagnoses of antisocial personality disorder and substance dependence. Further research using this analytical strategy could help identify the functional significance of individual differences in habituation.