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The current study investigated the performance of propensity score analysis with structural equation modeling in estimating the effect of students’ expectations about STEM career on college success using an illustrative subsample of the Longitudinal Study of High School of 2009. This study followed the methodology that is outlined by Leite et al., (2019), controlling selection bias by creating matched groups based on several confounders (i.e., sociodemographic, aspiration for science, and institutional characteristics). The findings showed significant average treatment effect (ATT) on treated individuals (i.e., students who expect to have STEM occupation by age 30 years) on post-secondary success. Race, SES, high school GPA, science identity, utility, and self-efficacy moderate the effect of students’ expectations about STEM occupation on college success.