Understanding the emotional profile of students during their training, as well as associated psychosocial factors such as optimism versus pessimism and self-esteem, is critical to improving student performance, especially in the post-pandemic period. In this study, 798 university students participated, belonging to the Degrees of Early Childhood and Primary Education, with a mean age of 24.52 years (±5.48). The following instruments were used: Wong Law Emotional Intelligence Scale (WLEIS-S), Life Orientation Test Revised (LOT-R) and the Rosenberg Self-Esteem Scale (RSES). The objective was to determine the predictive value of self-esteem on emotional intelligence and optimism vs. pessimism. A positive relationship between several dimensions of the instruments used (p < 0.01) were found. Moreover, the regression model predicted an association between emotional intelligence (use of emotions), pessimism and self-esteem. The practical consequences suggest the importance of the acquisition of emotional competences by university students is essential to obtain higher performances.