Background: Previous findings have shown that neuroticism is a higher-order vulnerability factor in the development and maintenance of sexual dysfunctions and can have an impact on the attentional processing of sexual stimuli; however, the influence of psychosexual dimensions on the early automatic phases of such cognitive processes has not been established yet.Aim: Examine the mediating role of sexual inhibition/excitation propensity in the relationship between neuroticism and automatic attention to visual erotica and identify the neuroelectric correlates of such a process. Methods: We analysed the answers provided by 58 individuals in a sociodemographic questionnaire, in the Neuroticism subscale of the NEO-Personality Inventory-Revised (NEO PI-R) and in the Sexual Inhibition/Excitation Scales (SIS/SES). Event-related potentials (ERP) P1, P2 and N2 were recorded during a modified oddball paradigm containing romantic and sexually explicit pictures. Parallel mediations were performed to simultaneously test the mediating role of sexual inhibition/excitation in the relationship between neuroticism and each ERP of interest. Outcomes: Findings revealed an indirect effect of neuroticism on automatic attention, via sexual inhibition due to threat of performance failure (SIS1), for both romantic and sexually explicit stimuli. This effect was only significant for component N2, which showed increased amplitudes and earlier latencies in participants with high SIS1, as a result of high neuroticism. This suggests that neuroticism is linked to SIS1 which, in turn, impacts how sexual cues are attentively perceived. The neuroelectric signal shows that the highest the SIS1 the more salient and prioritised are the sexual cues.Clinical Translation: Findings suggest that sexual stimuli, due to their emotional valence and arousal potential, could be perceived as virtually threatening by individuals with neuroticism, and trigger maladaptive strategies, such as a stress response. These results provide a better understanding of the relationship between personality and sexual cognition and could help fine-tune clinical interventions for those who experience sexual difficulties. Strengths and Limitations: This was one of the first studies to analyse the neuroelectric activity associated with automatic attention towards sexual stimuli, in relation to personality and sexual excitation/inhibition propensity. Nevertheless, the limited number of participants and the constraints posed by the laboratory apparatus demand caution in the generalization of the results. Conclusion: Our findings suggest that automatic attentional mechanisms can hold a close relationship to personality and sexual-related domains, and open new avenues of research in relation to other automatic cognitive phenomena related to human sexual behaviour.