A renewed interest in the study of character and virtue has recently emerged in the fields of Education and Psychology. The latest research has confirmed the association between virtuous consistent behaviours and academic positive outcomes. However, the motivational dimension of character (the intentions underlying the patterns of observed behaviours) has received little attention. This research aims to extend the knowledge on this topic by examining the predictive relationships between the behavioural and motivational dimensions of character, with reference to academic engagement, career self-doubt and performance of Spanish university students. A total of 183 undergraduates aged 18-30 (142 of whom were women) from the north of Spain completed specific parts of self-report questionnaires, including the Values in Action VIA-72, a Spanish translated and validated version of the Moral Self-Relevance Measure MSR, and the Utrecht Work Engagement Student Scale UWES-S9. The collected data were analysed using Structural Equation Modelling. The behavioural dimension of character (character strength factors of caring, self-control and inquisitiveness) showed positive associations with academic engagement and performance. The motivational dimension of character (phronesis motivation), was negatively related to career self-doubt. For the first time, the present study has provided support for the contribution of both dimensions of character to undergraduate academic outcomes.