Perceived motor competence (PMC) and physical literacy (PPL), in conjunction with actual motor competence (AMC) are relevant factors for engaging adolescents in active lifestyles. The main purpose of this study is to analyze the mediating role of PMC and PAM in the association between AMC and physical activity (PA) participation. In this study, 222 students (112 girls; 50.5%) aged 12 to 14 years-old participated voluntarily. By using structural equation modeling, the relationship between AMC and PA and the mediating influence of PMC and PPL on this relationship was analyzed. Model one, considering PMC (CFI = .97; RMSEA = .08; SRMR = .04) and model two with PPL (CFI = .99; RMSEA = .05; SRMR = .03) fitted satisfactorily. Therefore, it is not only important to promote AMC, but also to develop psychosocial and emotional factors such as PMC and PPL to promote PA participation among adolescents.