The aim of this study was to associate the epidemiology of whole body, peripheral, and central adiposity with sociodemographic characteristics, health-related behaviors, and biological maturation of adolescents from a Brazilian state capital. A cross-sectional school-based study was conducted in Florianopolis, Santa Catarina, Brazil with 818 adolescents aged 14 to 18 years, and 61.8% female. The peripheral adiposity was assessed by the triceps skinfold thickness and the central adiposity by the subscapular skinfold thickness, using cutoff greater than or equal to percentile 90 of the Centers for Disease Control and Prevention reference curve. Adolescents with high whole body adiposity were those showing skinfold thickness values above the reference percentile. Logistic regression analysis was applied using multivariable model. The prevalence of high whole body, peripheral, and central adiposity was 8.0%, 8.7%, and 10.3% for boys and 3.8%, 6.3%, and 11.1% for girls, respectively. Factors associated with this outcome in boys were overweight/obesity and low aerobic fitness (p < 0.05). Besides these factors, girls were also associated with excessive body fat, low paternal schooling, and puberty status (p < 0.05). Physical activity, sedentary behavior, and eating habits were not associated with this outcome. It was concluded that the main predictors of high body adiposity were overweight and low aerobic fitness in both sexes and low parental schooling and puberty status in females.