A prominent characteristic of externalizing psychopathology is the inability to suppress or modulate behavioral responses and impulses. These tendencies have been associated with cognitive indicators of inhibitory control (P3) and error processing (error-related negativity ERN and positivity Pe). However, the extent to which these trait-like components are characteristic of specific manifestations, or externalizing proneness more generally, remains unclear. Our study aimed to further contextualize externalizing behaviors by examining associations between distinct facets of externalizing symptoms and relevant behavioral phenotypes (substance use, aggression, pathological personality and internalizing symptoms) as well as electrophysiological and behavioral indices of inhibitory control (congruence and no-go P3, flanker interference, commission errors) and error processing (ERN and Pe, post-error slowing). Using a sample of community and jail dwelling offenders (N = 497), we used Confirmatory Factor Analyses to estimate a general externalizing factor (EXT), representing shared variance, and latent factors representing symptoms related to callous-aggression (CAL; conduct disorder and antisocial personality disorder) and alcohol and drug dependence (AD and DD). Additionally, a subset of participants (N = 89) had their brain activity recorded during a flanker task. Factor analyses supported general EXT and CAL factors; however, unique AD/DD overlapped highly with shared EXT, suggesting that DSM substance use symptoms in our study reflect more general problems with disconstraint/impulsivity rather than variance specific to substances. The general EXT was marked by behavioral correlates of impulsivity and negative affect, and laboratory task deficits in error monitoring, but with greater differential processing of inhibitory cues. The CAL specific factor was associated with affective shallowness phenotype, and, interestingly, laboratory measures of enhanced processing of inhibitory cues and error adjustment. This research has implications for understanding neurocognitive processes associated with distinct manifestations of disordered behavioral inhibition. •Factor analyses supported general externalizing and callous-aggression factors.•DSM substance use symptoms were mostly accounted for by shared externalizing.•Externalizing was marked by deficits in error processing, but not inhibitory control.•Callous-aggression was linked to shallow affect and enhanced cognitive control.