Although the built environment and certain psychosocial factors are related to adolescents’ active commuting to and from school (ACS), their interrelationships have not been explored in depth. This study describes these interrelationships and behavioral profiles via a self-organizing map (SOM) analysis. The sample comprised 465 adolescents from the IPEN (International Physical Activity and the Environment Network) Adolescent study in Valencia, Spain. ACS, barriers to ACS, physical self-efficacy, social support and sociodemographics were measured by questionnaire. Street-network distance to school, net residential density and street intersection density were calculated from the Geographic Information System. The clustering of the SOM outcomes resulted in eight areas or clusters. The clusters which correspond to the lowest and highest ACS levels were then explored in depth. The lowest ACS levels presented interactions between the less supportive built environments (i.e., low levels of residential density and street connectivity in the neighborhood and greater distances to school) and unfavorable psychosocial variables (i.e., low values of physical self-efficacy and medium social support for ACS) and good access to private motorized transport at home. The adolescents with the lowest ACS values exhibited high ACS environment/safety and planning/psychosocial barrier values. Future interventions should be designed to encourage ACS and change multiple levels of influence, such as individual, psychosocial and environmental factors.