Impulsivity is a multifaceted trait with substantial implications for human well-being. One facet of impulsivity is negative urgency, the tendency to act impulsively in response to negative affect. Correlational evidence suggests that negative affect magnifies impulsive behavior among individuals with greater negative urgency, yet causal evidence for this core pillar of urgency theory is lacking. To fill this gap in the literature, participants (N = 363) were randomly assigned to experience social rejection (a situation shown to induce negative affect) or acceptance. Participants then reported their subjective negative affect, completed a behavioral measure of impulsivity, and reported their negative urgency. Among individuals with relatively high and average negative urgency, social rejection increased their impulsive behavior through greater experiences of negative affect. These indirect effects were not observed among individuals relatively low in negative urgency. These findings suggest that negative urgency exists at the nexus of urgent dispositions and situations that elicit negative affect, which offers novel support for urgency theory.