Highly palatable foods play a salient role in obesity and binge-eating, and if habitually eaten to deal with intrinsic and extrinsic factors unrelated to metabolic need, may compromise adaptive coping and interpersonal skills. This study used event sampling methodology (ESM) to examine whether individuals who report eating palatable foods primarily to cope, to enhance reward, to be social, or to conform, as measured by the Palatable Eating Motives Scale (PEMS), actually eat these foods primarily for the motive(s) they report on the PEMS. Secondly this study examined if the previously reported ability of the PEMS Coping motive to predict BMI would replicate if the real-time (ESM-reported) coping motive was used to predict BMI. A total of 1691 palatable eating events were collected from 169 college students over 4 days. Each event included the day, time, and types of tasty foods or drinks consumed followed by a survey that included an abbreviated version of the PEMS, hunger as an additional possible motive, and a question assessing general perceived stress during the eating event. Two-levels mixed modeling confirmed that ESM-reported motives correlated most strongly with their respective PEMS motives and that all were negatively associated with eating for hunger. While stress surrounding the eating event was strongly associated with the ESM-coping motive, its inclusion in the model as a predictor of this motive did not abolish the significant association between ESM and PEMS Coping scores. Regression models confirmed that scores on the ESM-coping motive predicted BMI. These findings provide ecological validity for the PEMS to identify true-to-life motives for consuming palatable foods. This further adds to the utility of the PEMS in individualizing, and hence improving, treatment strategies for obesity, binge-eating, dietary nutrition, coping, reward acquisition, and psychosocial skills.