Both personality and motivational characteristics can be considered to estimate individuals’ potential for adjustment and development. That said, these characteristics are rarely studied in conjunction. In this study, we examine how personality and motivational characteristics relate one to the other and influence how students approach learning. More precisely, we analyzed the additive and interactive effects of two intimately related traits (extraversion and emotional stability) from the Big Five model of personality on five motivational dimensions reflecting academic expectations (sense of competence) and values (interest, utility, and mastery and performance goal orientations). Data was collected from a sample of 303 students in tenth and eleventh grade (108 boys and 195 girls; Mage = 16.275 years, SD = 1.149) in a French-Canadian public high school in the greater Quebec City area. Primary analyses included both bivariate correlation and hierarchical regression analyses. Correlations indicated that emotionally stable students were more interested in learning. Hierarchical regression showed that emotionally stable students were more likely to exhibit a performance goal orientation, especially when they were extroverted. These analyses also revealed that emotionally stable students were more interested in learning, especially when they had a strong sense of competence. Results are discussed in light of the limited but relevant existing literature.