Purpose: Physical literacy is understood to be important for adolescents’ behavioral and psychological wellness. Yet, to date, limited empirical data exist to support such reasoning. Addressing this gap, the present study examined relationships between physical literacy and early adolescents’ physical education engagement, leisure-time exercise behavior, and psychological well-being. Methods: The physical literacy level of 187 early adolescents (Mage = 12.84, SD = 0.55, girls = 99) was measured using the Canadian Assessment for Physical Literacy. One week later, data pertaining to standardized measures of engagement in physical education, leisure-time exercise behavior, and psychological well-being were collected. Results: Structural equation modeling revealed that physical literacy was positively correlated with physical education engagement, leisure-time exercise, positive affect, and vitality, whereas it was negatively correlated with negative affect. Conclusion: The findings from this work substantiate the contention that physical literacy has manifold benefits for early adolescents’ behavioral and psychological wellness.