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We examined whether autonomy satisfaction and frustration could be empirically distinguished and had different predictive relationships with students’ academic outcomes and school burnout. Results based on a group of 1639 Chinese adolescent students revealed that autonomy satisfaction and frustration were two distinguishable constructs with unique predictive utilities. Specifically, autonomy satisfaction positively predicted persistence and negatively predicted procrastination, leading to higher achievement and lower school burnout. In contrast, autonomy frustration positively predicted procrastination and negatively predicted persistence, resulting in higher school burnout and lower achievement. Additionally, autonomy frustration directly predicted school burnout, whereas autonomy satisfaction mitigated it. These findings underscore the importance of differentiating autonomy satisfaction and frustration when predicting students’ educational outcomes.