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This study examined the co-development of prosocial behaviors and peer relationships from grades 1 to 12 and their association with post-secondary education enrollment among academically at-risk children (N = 784). Using data from a 12-year longitudinal study and a bivariate latent growth model, we found that prosocial behaviors remained stable, whereas peer relationships significantly improved over time. Prosocial behaviors and peer relationships were positively correlated at both intercept and slope, indicating reciprocal development. Importantly, both the initial level and growth of prosocial behaviors significantly predicted post-secondary enrollment. These findings underscore the importance of early and sustained support for prosocial development to foster positive peer relationships and improve educational outcomes, offering key implications for interventions aimed at increasing college enrollment.