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We examine the impact of a deeper learning program on students’ postsecondary education (PSE) enrollment by investigating both mediating and moderating mechanisms. To understand whether and why deeper learning influences PSE enrollment, we examine students’ self-determination as a potential mediator linking program participation to PSE enrollment, and we examine contextual factors to identify for whom the program is most effective. Results indicate a significant association between participation in deeper learning and PSE enrollment. Structural equation modeling further shows that deeper learning has a significant effect on students’ self-determination; however, the association between self-determination and PSE enrollment is not significant, potentially reflecting heterogeneity in program impacts. Moderation analyses indicate that deeper learning effects are impactful for students with higher prior achievement.