Background: Few studies have examined the association between 24-hour movement behaviors and health in children in their first 2 years of primary school. This study aimed to examine how 24-hour movement behavior compositions at age 6 were related to body mass index (BMI), waist circumference, and internalizing and externalizing symptoms at ages 6 and 10. Methods: A subsample of 361 children from the HealthNuts cohort study with valid accelerometer data was included in the cross-sectional analysis. Of these, 279 had longitudinal data for social-emotional outcomes and 113 had longitudinal anthropometric data. Children’s 24-hour movement behaviors (ie, sleep, sedentary time, light-intensity physical activity, and moderate- to vigorous-intensity physical activity [MVPA]) were assessed over 8 days using accelerometery and activity logs. BMI z score and waist circumference were assessed using standardized protocols, and parents reported on their child’s internalizing and externalizing behaviors. Cross-sectional and longitudinal associations were estimated using compositional data analysis and compositional isotemporal substitution analysis. Results: Overall, 24-hour movement behaviors were significantly related to internalizing symptoms cross-sectionally and longitudinally and BMI z-score cross-sectionally. Results from compositional isotemporal substitution models indicated that replacing sedentary time or light-intensity physical activity with MVPA was associated with fewer internalizing symptoms at ages 6 and 10. Replacing time spent sedentary and in light-intensity physical activity or MVPA with sleep was associated with lower BMI z score at age 6. Conclusion: Spending more time in MVPA relative to other movement behaviors is associated with fewer internalizing symptoms. In additional, spending more time sleeping is associated with lower BMI z score and waist circumference in children.