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The supply of and performance in STEM pipeline has arouse much attention, and how to encourage participation of people from underrepresented groups in STEM in postsecondary education is also a concern in the U.S.. Based on Expectancy-Value Theory, this study aims to examine the relationship between students' motivation in Math and Science in high school and their postsecondary STEM performance. Using the HSLS:09 dataset and employing Principal Component Analysis and Multivariate Regression, it found that students' motivation in math and science in high school is positively associated with their postsecondary STEM GPA. The results vary across gender, race and socio-economic groups. These findings advanced the understanding of STEM pipeline, and offered policy implications to enhance students' STEM motivation and outcomes.