Resilience is a critical ability to cope successfully with stressful circumstances. Sensitivity to negative stimuli and perceived control both independently impact stress-related vulnerabilities or resilience. However, the relationships among them remain unclear. This study aimed to examine the association between negative emotion sensitivity and psychological resilience, and whether this association is influenced by perceived internal control. Ninety-one healthy young adults passively viewed negative and neutral pictures while electroencephalogram (EEG) data were recorded. The Late Positive Potential (LPP) was measured as an indicator of sensitivity to negative emotional stimuli. Perceived internal control and psychological resilience were assessed through self-reported questionnaires. Results showed that increased sensitivity to negative stimuli, reflected by larger LPP amplitudes in response to unpleasant versus neutral pictures, was associated with lower psychological resilience after controlling for gender and age. Furthermore, perceived internal control significantly mediated the relationship between LPP amplitudes and psychological resilience, with larger LPP amplitudes linked to lower perceived internal control, which in turn related to lower resilience. These findings suggest that heightened sensitivity to negative stimuli is associated with reduced resilience, with perceived internal control serving as a potential connecting mechanism.