Psychological flexibility (PF), the core process of Acceptance and Commitment Therapy (ACT; a third-wave cognitive-behavioral therapy), is the ability to stay focused on the present moment and intentionally engage in value-driven behavior despite experiencing difficult thoughts or feelings. This multifaceted construct includes components that target processes occurring both internally (e.g., cognitive processes) and behaviorally (e.g., value-consistent actions). Psychological flexibility has been applied to studies of adjustment in non-clinical samples and may be beneficial for college students as individuals navigate novel developmental stressors. Despite evidence suggesting the benefits of PF for psychological distress, additional work is needed to examine the potential of PF to foster adaptive functioning. The current study builds on previous research by a) conceptualizing distinct internal and behavioral components of PF as promotive factors and b) emphasizing competence-focused outcomes. This research examined the influence of components of PF over the course of an academic semester. A sample of college students (N = 250) completed self-report measures online at the beginning (Time 1) and end (Time 2) of a college semester. Measures included components of PF, competence, and demographic and academic information. Structural equation modeling was used to examine associations between components of PF at Time 1 on competence at Time 2, while accounting for the influence of competence at Time 1. Findings suggested that within the social domain, value-consistent action at Time 1 was associated with increased social competence at Time 2. Additional results indicated that baseline competence accounted for associations between components of PF and Time 2 competence. Implications for the dissemination of ACT-informed efforts to promote positive adjustment among college students are reviewed, and future research directions are discussed.