Impulsivity is associated with cigarette smoking, but the nature of this relationship and the mechanisms that maintain it are relatively unknown. The relationship has often been thought to reflect appetitive processes, but research suggests that an affective pathway exists as well. The present study tested the effect of impulsivity on affective responses to an environmental smoking cue. Adult smokers (N = 62) were exposed to a neutral cue and a smoking cue in separate experimental sessions in a repeated-measures design. Mixed-effects regression analyses showed that larger postexposure increases in negative affect were associated with high scores on 2 facets of impulsivity: urgency, t(179) = 6.16, p < .001, and sensation seeking, t(179) = 4.75, p < .001. Heightened impulsivity was associated with lower levels of positive affect generally but not with positive affective responses to cue exposure. Findings provide support for the existence of a negative affective pathway linking impulsivity and cigarette smoking, and they suggest that this pathway may be specific to the urgency and sensation-seeking components of impulsivity.