National studies indicate that units and level of rigor in mathematics coursework are the strongest predictors of college enrollment. However, for young Black women there are often structural barriers impeding access to rigorous mathematics coursework, potentially impinging on postsecondary enrollment. In the present study the authors analyze the relationship between math self-efficacy and student propensity to enroll in any postsecondary institution as well as the relationship between math self-efficacy and the propensity enroll in four-year postsecondary institutions for Black women high school students. To do so, the authors use the National Center for Education Statistics (NCES) Educational Longitudinal Survey of 2002 and find that for young Black women students, having a higher math self-efficacy is positively associated with enrollment in a four-year institution. Unfortunately, their math self-efficacy erodes over time and lower mathematics self-efficacies are negatively associated with postsecondary enrollment. As students who start in a four-year environment are more likely to complete the baccalaureate degree, encouraging mathematics self-efficacy development is a logical step toward improving Black women's educational attainment.