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Rural students represent nearly one-fifth of the U.S. student population, yet they remain underserved in STEM education and underrepresented in postsecondary STEM degree programs. This study examines how STEM opportunities to learn (OTL), motivational beliefs, academic preparation, and college enrollment of rural students vary across geographical remoteness areas, leveraging restricted-use data from the High School Longitudinal Study of 2009 (HSLS:09) linked to the Common Core of Data (CCD). Drawing on theoretical perspectives of opportunity-to-learn, situated expectancy-value theory, and spatial inequality, this study conceptualizes STEM pathways as both academic and motivational processes embedded in geographic context. Results show that rural-fringe students have opportunities largely comparable to suburban peers, but students in rural-distant and especially rural-remote schools face severe inequities in access to advanced STEM coursework and extracurricular enrichment. These OTL disparities are associated with lower STEM motivation, weaker STEM academic preparation, and reduced enrollment in four-year STEM programs. Block-entry regression models indicate that demographic characteristics account for part of the suburban–rural gaps, while high school STEM OTL accounts for additional variation in STEM academic preparation, and motivational and preparation factors jointly account for STEM college enrollment disparities. This study provides the first nationally representative, longitudinal evidence of how geographical remoteness links to unequal STEM pathways, highlighting the importance of context-specific policies and interventions to expand advanced coursework, extracurricular opportunities, college enrollment in STEM for rural students in distant and remote areas.