This study aimed to analyze the differences between active commuting to school (ACS) and non-ACS in cognitive performance (CP), and the association of ACS duration with CP. This cross-sectional study included 370 adolescents (males n = 170), with a mean age of 15.28 ± 2.25 years. CP was assessed through an interview, and ACS, extracurricular physical activity, and socioeconomic status was assessed by self-report. Body composition was assessed using the FitnessGram test battery. One in two adolescents did ACS (51.6%). ACS was associated with boys (53.9%), younger adolescents (14.91 ± 2.15 vs. 15.69 ± 2.29), those having school social support (55.0%), and those doing one or more extracurricular physical activities (53.6%), compared to non-ACS participants (p < 0.05). The analysis of covariance, after controlling for age, sex, school social support, and participation in extracurricular physical activity, showed an effect of ACS on the total cognitive score (F_(2,362) = 3.304, p < 0.05). The CP was higher in adolescents with more than 30 min of ACS than non-ACS (p < 0.05). The influence of ACS duration can be seen in the dimensions of inductive reasoning (ß = 0.134, t = 2.587, p < 0.05) and working memory (ß = 0.130, t = 2.525, p < 0.05). The role of ACS for CP, as well as guidelines for future research, are discussed.