Sexual minority students such as those identifying as lesbian, gay, or bisexual, as well as those identifying with emerging self-labels (e.g., queer) face a host of risk factors in high school that can potentially compromise educational excellence, particularly in rigorous academic disciplines. The current study advances the area of diversity within science, technology, engineering, and mathematics (STEM) education by empirically exploring the question: Is there a gap in STEM education participation based on sexual minority status? After reviewing the relevant research, we employed hierarchical linear modeling to explore advanced math and science course-taking patterns among a nationally representative sample of students from the National Longitudinal Study of Adolescent Health. Results of this initial exploratory study suggest that advanced math and science course-taking does not vary significantly based on sexual minority status once a host of individual and school factors are included. The null findings advance the discussion of equity and excellence in STEM education as it relates to vulnerable populations. The article ends with a discussion of limitations and directions for future research.