In this study, the authors used the Facial Action Coding System (FACS; P. Ekman & W. V. Friesen, 1978) to examine the immediate facial responses of abstinent smokers exposed to smoking cues. The aim was to investigate whether facial expressions thought to be linked to ambivalence would relate to more traditional measures of ambivalence about smoking. The authors adapted N. A. Heather's (1998) definition of ambivalence about smoking, which emphasizes difficulty in refraining from smoking despite intentions to do so. Ambivalence expressed during smoking cue exposure was operationalized as the simultaneous occurrence of positive and negative affect-related facial expressions. Thirty-four nicotine-deprived dependent smokers were presented with in vivo smoking cues, and their facial expressions were coded using FACS. Participants also completed self-report measures related to ambivalence about smoking. Smokers who displayed ambivalent facial expressions during smoking cue exposure reported significantly higher scores on measures of smoking ambivalence than did those who did not display ambivalent facial expressions.