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Using the nationally representative High School Longitudinal Study of 2009, we investigate whether and how high school contexts affect students’ STEM major choice. We hypothesize that STEM-intensive high school contexts foster students’ STEM interests and thus influencing their college STEM major choices. Multiple imputation and sample weights were used to enhance the data. We estimated a structural equation model to predict postsecondary STEM major choice. Results indicate that students from high schools with more AP science courses are more likely to choose STEM majors, and students’ science interest mediates the effect from the AP science course to major choice. Implications for K-12 and postsecondary policy and scholarship are discussed.