Background: Recent physical activity research is limited by intention–behavior discordance and is beginning to recognize the importance of automatic processes in exercise. The purpose of the current study was to examine the role of multidimensional exercise self-efficacy (SE), explicit–implicit evaluative discrepancies (EIEDs) for health, and appearance on the intention–behavior gap in exercise. Methods: A total of 141 middle-aged inactive participants (mean age = 46.12 [8.17] y) completed measures of intentions, SE, and explicit and implicit evaluations of exercise outcomes. The participants were classified as inclined actors (n = 107) if they successfully started the exercise program and inclined abstainers (n = 35) if they were not successful. Results: The inclined actors and abstainers did not differ on intentions to exercise; however, the inclined actors had higher coping SE and lower EIEDs for health. In addition, the coping SE (Exp [β] = 1.03) and EIEDs for health (Exp [β] = −0.405) were significant predictors of being an inclined actor. Conclusions: The interaction between explicit and implicit processes in regard to health motives for exercise appears to influence the successful enactment of exercise from positive intentions. As most physical activity promotion strategies focus on health as a reason to be active, the role of implicit and explicit evaluations on behavioral decisions to exercise may inform future interventions.