The literature documents that personality characteristics are associated with healthy lifestyles, including smoking. Among positive traits, Positivity (POS), defined as a general disposition conducive to facing experience under a positive outlook has shown robust associations with psychological health. Thus, the present study investigated the extent to which POS is able to predict (i) relapse after quitting smoking and (ii) the desire to smoke again. All participants (481) had previously attended a Group Counselling Program (GCP) for Smoking Cessation (from 2005 through 2010). They were contacted through telephone interview. Among participants, 244 were ex-smokers (age: years 56.3 ± 10.08, 52% female) and 237 were still-smokers (age: years 55.0 ± 9.63; 63.5% female). The association of POS with “craving to smoke” levels was assessed with multivariate linear regression analysis while controlling also for important differences in personality such as conscientiousness and general self-efficacy, as well as for gender and age. Results showed that POS was significantly and negatively associated with smoking status and with craving to smoke. Among covariates (i.e., conscientiousness, generalized self-efficacy), gender was associated with smoking status and with craving to smoke. Altogether these findings corroborate the idea that POS plays a significant role in sustaining individuals' efforts to quit smoking.