Many countries implement a double-shift schooling system, offering morning or afternoon shifts, driven by diverse factors. Young people with ADHD may face educational problems attending morning shifts compared to afternoon shifts. To investigate this, we used data from a Brazilian school-based cohort (n = 2.240, 6–14 years old, 45.6% female; 50.2% in the morning shift; 11.2% with ADHD). ADHD was determined by child psychiatrists using semi-structured interview. Educational outcomes were measured cross-sectionally and three years later (80% retention) and included reading and writing ability, performance in school subjects, and any negative school events (repetition, suspension, or dropout). Generalized regression models tested the interaction between ADHD and school shift and were adjusted for age, sex, race/ethnicity, intelligence, parental education, socioeconomic status, and site. Attrition was adjusted with inverse probability weights. We used two dimensional measures of attentional problems as sensitivity analysis. ADHD and morning shift were independently associated with lower reading and writing ability and with higher odds for negative school events cross sectionally. ADHD independently predicted lower performance in school subjects and higher negative school events at follow-up. Interaction was found only at the cross-sectional level in a way that those studying in the afternoon present better educational outcomes compared with those studying in the morning only if they have lower ADHD symptom. Thus, ADHD was not associated with poorer educational outcomes among those studying in the morning. However, participants studying in the afternoon with lower levels of attentional problems presented better educational, despite these associations fade away over time.