Background: Participation in physical activity (PA) is a modifiable factor that contributes to academic success, yet the optimal dose (ie, frequency) and mechanisms underlying the effect require further exploration. Methods: Using data from 19,886 elementary and 11,238 secondary school students across Ontario, Canada, this study examined associations between PA participation frequency, academic achievement, and inattention and hyperactivity. Results: Among elementary students, there was a positive association between PA frequency and academic achievement. Participating in 1 to 2 days per week of PA related to higher academic achievement compared with no days, whereas 7 days per week had the largest associations. For secondary students, a minimum of 3 to 4 days per week was associated with higher academic achievement with no significant benefit of additional days. Indirect effects of inattention and hyperactivity were found for both groups, suggesting that the benefits of PA on academic achievement may be partly explained by reductions in inattention and hyperactivity, especially for secondary school students. Conclusion: Students may experience academic benefits from PA even if they are not meeting the guidelines of exercising daily. These benefits may occur, in part, through reductions in inattention and hyperactivity. Further work is needed to determine the temporality and mechanism of these associations.