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STEM (Science, Technology, Engineering and Mathematics) education and industry, civic engagement, and basic skills are all important indicators not only for the economy but also for societal well-being. However, the associations between STEM background, volunteering as a form of civic engagement, and literacy skills are yet to be examined in the U.S. We analyzed the 2012/2014/2017 Program for International Assessment of Adult Competencies (PIAAC) Restricted Use file, focusing on the U.S. adult population aged 25 years and older (n = 8,690). Results from the structural equation model showed that possible reasons for the higher volunteer participation rate by adults with STEM backgrounds may be due to their higher basic skills. Theoretical explanations and preliminary education policy implications are discussed.