We examined whether autonomy satisfaction and frustration could be empirically distinguished and had different predictive relationships with students' academic motivation and achievement in maths and English. Results based on a group of 3142 Chinese adolescent students revealed that autonomy satisfaction and frustration were two distinguishable constructs and demonstrated distinct predictive utility. Specifically, satisfaction of autonomy was positively associated with self-efficacy, which in turn, led to higher achievement. Furthermore, autonomy satisfaction was positively linked to interest value. In contrast, frustration of autonomy was positively associated with effort cost, which subsequently undermined achievement. Furthermore, these patterns were highly consistent across two subject domains. Findings of the present study highlight the importance of differentiating between autonomy satisfaction and frustration when predicting students' academic outcomes.