Adolescent development is not only shaped by the mere passing of time and accumulating experience, but it also depends on pubertal timing and the cascade of maturational processes orchestrated by gonadal hormones. Although individual variability in puberty onset confounds adolescent studies, it has not been efficiently controlled for. Here we introduce ultrasonic bone age assessment to estimate biological maturity and disentangle the independent effects of chronological and biological age on adolescent cognitive abilities, emotional development, and brain maturation. Comparing cognitive performance of participants with different skeletal maturity we uncover the impact of biological age on both IQ and specific abilities. With respect to emotional development, we find narrow windows of highest vulnerability determined by biological age. In terms of neural development, we focus on the relevance of neural states unrelated to sensory stimulation, such as cortical activity during sleep and resting states, and we uncover a novel anterior-to-posterior pattern of human brain maturation. Based on our findings, bone age is a promising biomarker of adolescent maturity.