Recent literature has recognized the advantageous role of low-arousal positive affect such as feelings of peacefulness and internal harmony in collectivist cultures. However, limited research has explored the benefits of low-arousal affective states in the educational setting. The current study examined the link of peace of mind (PoM) to academic motivation (i.e., amotivation, controlled motivation, and autonomous motivation) and academic achievement among 525 Filipino high school students. Findings revealed that PoM was positively associated with academic achievement β = .16, p < .05, autonomous motivation β = .48, p < .001, and controlled motivation β = .25, p < .01. As expected, PoM was negatively related to amotivation β = –.19, p < .05, and autonomous motivation was positively associated with academic achievement β = .52, p < .01. Furthermore, the results of bias-corrected bootstrap analyses at 95% confidence interval based on 5,000 bootstrapped resamples demonstrated that peace of mind had an indirect influence on academic achievement through the mediating effects of autonomous motivation. In terms of the effect sizes, the findings showed that PoM explained about 1% to 18% of the variance in academic achievement and motivation. The theoretical and practical implications of the results are elucidated.