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.