Introduction: The Wisconsin Inventory of Smoking Dependence Motives (WISDM) is a multidimensional measure of smoking motives that was developed to facilitate research aiming to refine the nomological network surrounding tobacco dependence. Recent evidence suggests that a composite of four subscales, termed the Primary Dependence Motives (PDM), may represent core features of advanced addiction, while the remaining nine subscales (Secondary Dependence Motives; SDM) represent instrumental motives for cigarette use that may be relevant at any stage of smoking. Methods: A sample of 255 smokers (all regular alcohol users) participated in an ecological momentary assessment study in which they monitored smoking behavior and related experiences for 21 days. Multilevel regression analyses tested how PDM and SDM predicted daily smoking rate, cigarette craving, and appraisals of pleasure and relief of unpleasant feelings from smoking. Results: When PDM and SDM were entered simultaneously, only PDM was related to daily cigarette count, and only SDM predicted reports of craving and relief from unpleasant feelings from smoking. SDM was associated with reports of greater pleasure from smoking and PDM was associated with lower pleasure ratings. The Fagerström Test for Nicotine Dependence (FTND) was related to daily smoking rate and craving, but WISDM composites contributed incremental prediction. Conclusions: The findings confirm that PDM indexes heavier use that is relatively unrelated to immediate consequences of smoking. SDM is not uniquely related to smoking heaviness, but is associated with craving and reports of pleasure and relief of unpleasant feelings derived from smoking during ad lib use. Implications: This study extends the evidence for the distinction between the WISDM PDM and SDM. PDM scores are associated with heavier smoking and are relatively unrelated to immediate consequences of smoking. SDM is more strongly related to craving and reports of smokingderived pleasure and relief of unpleasant feelings during ongoing use in daily life.