Background: Despite the frequent comorbidity of affective and addictive disorders, the significance of affective dysregulation in problematic pornography use (PPU) is commonly disregarded. The objective of this study is to investigate whether individuals with PPU demonstrate increased sensitivity to negative emotional stimuli in comparison to healthy controls (HCs). Methods: Electrophysiological responses were captured via event-related potentials (ERPs) from 27 individuals with PPU and 29 HCs. They completed an oddball task involving the presentation of deviant stimuli in the form of highly negative (HN), moderately negative (MN), and neutral images, with a standard stimulus being a neutral kettle image. To evaluate participants' subjective feelings of valence and arousal, the Self-Assessment Manikin (SAM) was employed. Results: Regarding subjective evaluations, individuals with PPU indicated diminished valence ratings for HN images as opposed to HCs. Concerning electrophysiological assessments, those with PPU manifested elevated N2 amplitudes in response to both HN and MN images when contrasted against neutral images. Additionally, PPU participants displayed an intensified P3 response to HN images in contrast to MN images, a distinction not evident within the HCs. Discussion: These outcomes suggest that individuals with PPU exhibited heightened reactivity toward negative stimuli. This increased sensitivity to negative cues could potentially play a role in the propensity of PPU individuals to resort to pornography as a coping mechanism for managing stress regulation.