In this study we examined the associations between perceived emotional intelligence, dispositional optimism/pessimism and psychological well-being. In addition to correlational analyses, we examined a model by structural equation modeling (SEM). The study of psychological well-being in the field of positive psychology from the paradigmatic approach to happiness developed by Ryff and Singer (Psychother Psychosomat 65(1):14–23, 1998) is very important and essential, due in part to the lack of studies analyzing the predictors of Ryff’s PWB model by contemplating emotional and cognitive factors. In this framework, our study examines the possible role of optimism and PEI as possible predictors of the psychological well-being dimensions proposed by Ryff, with a specific pattern of relationships as a model. Our results show positive relationships between clarity and emotional regulation and the psychological well-being components. With regard to dispositional optimism versus pessimism, positive relationships were found between optimism and psychological well-being dimensions and negative relationships between pessimism and dimensions of psychological well-being. Our model also includes some relationships, not initially raised, between the dimensions of perceived emotional intelligence and some dimensions of psychological well-being. Our results suggest relationships between emotional attention and purpose in life as well as with personal growth dimensions of psychological well-being. Implications and limitations are discussed.