Background: Research has demonstrated associations between pubertal development and brain maturation. However, existing studies have been limited by small samples, cross-sectional designs, and inconclusive findings regarding coupling directionality and sex differences. Methods: We examined the longitudinal temporal coupling of puberty status assessed using the Pubertal Development Scale (PDS) and magnetic resonance imaging (MRI)-based brain grey and white matter structure. Our sample consisted of 8,896 children and adolescents at baseline (mean age = 9.9) and 6,099 at follow-up (mean age = 11.9) from the Adolescent Brain and Cognitive Development (ABCD) Study. Results: Applying multigroup Bivariate Latent Change Score (BLCS) models, we found that baseline pubertal status predicted the rate of change in cortical thickness among females only, while it predicted rate of change in cortical surface area for both males and females, with a significantly stronger association for females. For cortical surface area, we also found a correlation between baseline pubertal status and area and co-occurring changes over time, with both associations present in males only. Diffusion tensor imaging (DTI) analysis revealed correlated change between pubertal status and fractional anisotropy (FA) for both males and females, but no significant associations for mean diffusivity (MD). Conclusions: Our results suggest that pubertal status in early adolescence predicts cortical maturation, and that the strength of the associations differ between sex. Further research is needed to understand how the associations between puberty and brain maturation are related to environmental and lifestyle factors, and the impact on mental health.