Impulsivity and cognitive function are essential for understanding behavioral regulation, particularly in relation to health-risk behaviors like substance use, physical activity, and academic performance. This study examined the factor structure underlying executive function in adolescents using the UPPS-P Impulsive Behavior Scale and NIH Toolbox Cognition Battery. We explored how parental monitoring moderates, and peer network health and perceived stress mediate, relationships between cognitive function and outcomes such as BMI, physical activity, and academic performance. Exploratory factor analysis (EFA) on 2228 observations identified a four-factor model (BIC = −97.92, RMSEA = 0.040, TLI = 0.936), validated by confirmatory factor analysis (CFA) (CFI = 0.961, RMSEA = 0.055). Structural equation modeling (SEM) on 5902 observations showed that parental monitoring moderated Factor 1 (adaptive impulsivity) in relation to physical activity and academic performance, while peer network health mediated Factor 2 (emotional impulsivity) effects on BMI and physical activity. This model underscores the influence of peer relationships, parental involvement, and stress on cognitive, health, and academic outcomes, suggesting that interventions enhancing peer support, reducing stress, and promoting healthy behaviors may improve adolescent well-being.