Previous studies demonstrated that boredom leads to increased self-administration of painful electric stimulation, a proxy for non-suicidal self-injury (NSSI). However, in these experimental studies, participants had no behavioral alternatives besides electric stimulation to break the monotony. A first aim in the current experimental study was to examine whether boredom still leads to self-administering aversive stimuli when positive behavioral alternatives are present. This boredom effect was furthermore compared to an anger induction. The second aim was to examine whether history of NSSI and negative urgency (i.e., the tendency to engage in impulsive action in response to negative emotions) positively moderate the link between boredom and self-administered aversive stimuli. In a between-subjects design using college students (N = 129), participants were randomly assigned to one of three emotion induction writing tasks (i.e., boredom, anger, neutral), during which frequency of self-administered positive (chirping birds) and aversive (screaming pig) sounds was measured. The latter was used as a proxy for NSSI behavior. Results showed that boredom led to increased selection of aversive sounds compared to the neutral and anger conditions, despite the presence of a positive alternative (i.e., positive sounds). No difference in frequency of selecting the aversive sounds was observed between the anger and neutral condition. Neither history of NSSI nor negative urgency moderated the effect of condition on self-administered aversive stimuli. The current results tentatively support a causal and specific link between boredom and NSSI, and warrant further examination of the role of boredom in maladaptive behaviors such as NSSI.