Using the self-determination theory (SDT), this study sought to understand motivational profiles and their links to psychological learning attributes. Participants were 90 secondary three (grade 9) students, aged 15 to 16 years old, from an elite all-girls school in Singapore. Hierarchical cluster analysis revealed three clusters of students with distinct motivational profiles. MANOVA, ANOVA and post hoc tests showed that the three clusters differed significantly in self-efficacy, intrinsic task value, effort and enjoyment in learning. A "highly motivated" cluster characterised by high introjected, identified and intrinsic regulations was found to be most adaptive, with the "highly motivated" cluster being associated with the most optimal psychological learning attributes. An "unmotivated" cluster characterised by high amotivation was found among this sample of high-ability students, with the "unmotivated" cluster being the least adaptive. The importance of understanding how the different motivational regulations were combined to influence psychological learning attributes was discussed.