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This paper examines public–Catholic gap in STEM opportunity to learn in the US using Mahalanobis-distance matching and adjacent categories models. Consistent with prior studies, there are significant public–Catholic differences in math and science course sequence level and total credits earned. However, we find that these gaps are largely accounted for by selection processes among students of differing family background. Moreover, we find that the Catholic school advantage in STEM opportunity to learn differs by subject; Catholic school students are more likely to enroll in advanced math courses relative to middle-level courses, while their advantage in science is concentrated in the middle of the course-taking hierarchy.