Abstract Background Further research is required to explore the associations between 24-h movement behaviours and health outcomes in the paediatric population. Therefore, this study aimed to examine the associations between novel data-driven 24-h activity metrics and adiposity among children and adolescents. Methods The sample included 382 children (8–13 years) and 338 adolescents (14–18 years). The average acceleration (AvAcc) of activity, intensity gradient (IG), and metrics representing the initial acceleration for the most active time periods of the 24-h cycle were calculated from raw acceleration data. Adiposity measures included body mass index z-score, fat mass percentage (FM%), and visceral adipose tissue (VAT). Data analysis was performed using multiple linear regression adjusted for wear time, sex, maternal education level, and maternal overweight and obesity. Results Children demonstrated higher values in all 24-h activity metrics than did adolescents (p < 0.001 for all). For children, the initial acceleration for the most active 2, 5, 15, and 30 min of the 24-h cycle were negatively associated with FM% (p ≤ 0.043 for all) and VAT (p <0.001 for all), respectively. For adolescents, the IG was negatively associated with FM% (p = 0.002) and VAT (p = 0.007). Moreover, initial acceleration for the most active 2, 5, 15, 30, 60, and 120 min were associated with FM% (p ≤ 0.007 for all) and with VAT (p ≤ 0.023 for all). Conclusions The intensity distribution of activity and initial acceleration for the most active 2, 5, 15, 30, 60, and 120 min within the 24-h cycle are beneficial for the prevention of excess adiposity in the paediatric population.