We investigated psychopathy from the neurobiological perspective of reinforcement sensitivity theory (RST). In contrast to previous semantically derived self‐report scales, we operationalised RST systems neurally with evoked electroencephalography (EEG). Participants were from a community sample weighted towards externalising psychopathology. We compared the Carver & White Behavioural Inhibition System (BIS)/Behavioural Approach System (BAS) scales with EEG responses associated with RST's systems of goal conflict (aka ‘behavioural inhibition’), repulsion/outcome conflict (aka ‘fight/flight/freeze’) and attraction (aka ‘approach’). Bivariate correlations and multiple regression analysis yielded results generally consistent with past literature for associations between psychopathy and the self‐report BIS/BAS scales. There were some differences from self‐report associations with neural measures of RST. With EEG measures, (1) no meaningful associations were observed between any psychopathy scales and the attraction system; (2) affective‐interpersonal traits of psychopathy were negatively associated with goal conflict; (3) disinhibition‐behavioural traits of psychopathy were negatively associated with goal conflict but, unexpectedly, positively associated with outcome conflict. These results indicate frontal‐temporal‐limbic circuit dysfunction in psychopathy as specific domains were linked to neural deficits in goal conflict processing, but there was no evidence for deficits in attraction‐related processes.