Cue-reactivity studies have shown that when consumers are exposed to a substance-related stimulus, potential tobacco use contributes significantly to craving and motivational drive. Although the motivational response to cues signaling tobacco availability has been widely studied, less is known about physiological reactivity to perceived cigarette availability. The aim of the present study was to examine the outcome-related negativity (ORN) evoked by stimuli that signal potential tobacco use in abstinent and sated smokers. The ORN is an event-related potential (ERP) component that reflects the emotional and motivational aspects of reward processing and is modulated by motivational value of reward. Thirty-two such smokers performed two distinct and comparable versions of a gambling task, under conditions of abstinence and satiation. The analysis of variance (ANOVA) analysis revealed that ORN amplitude was larger in abstinent than satisfied smokers on those trials in which tobacco could be used. Differences were significant at the Fz electrode (p < .01) and approached significance at the Cz (p = .061) and Pz (p = .059) electrodes. Moreover, ORN amplitude predicted subjective indices of desire and positive effects from smoking, but only in the abstinence condition. These findings suggest that perceived cigarette availability might influence physiological reactivity in smokers who are nicotine deprived. They also suggest that the ORN component may be related to the motivational mechanisms involved in addictive behavior.