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Motivational beliefs are essential in understanding adolescents’ achievement and choices. Drawing on expectancy-value theory, this study examined the relations among adolescents’ math and science motivational beliefs, their STEM achievement and choices in high school, and their STEM major choices in college. Using nationally representative data, this study found that adolescents’ math and science motivational beliefs at the beginning of high school were associated with their STEM achievement and choices throughout high school and their major choices in college. We found that female and first-generation college students had lower self-concept of ability and were less likely to pursue a STEM major. This study provided insights for educational policymakers and practitioners who are seeking to promote equity in the STEM field.