Brazil has been the benchmark for volleyball performance for at least two decades, providing a unique context to examine expertise development. This study examined the variation in body size, functional capacities, motivation for achievement, competitiveness, and deliberate practice of youth volleyball players associated with differences in biological maturity status, chronological age, and accumulated deliberate volleyball practice, adopting a Bayesian multilevel modeling approach. We considered 68 female and 94 male adolescent players (14.2 years, 90% confidence interval: 12.7 to 16.0). Players were grouped by the onset of deliberate volleyball practice as related to biologic maturation milestones [pre-puberty deliberate practice onset (12% of the sample), mid-puberty deliberate practice onset (51% of the sample), and late-puberty deliberate practice onset (37% of the sample). There was substantial variation in body dimensions and functional performance by gender. There was no variation by gender for motivation for deliberate practice and motivation for achievement and competitiveness. The young volleyball players appeared to be highly motivated and committed to deliberate practice, achievement, and competitiveness. Alignment of chronological age, biological maturation, and accumulated training experience allow more in-depth insights into young volleyball players’ development, providing sounder support for coaches´ decisions.