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Drawing from four theoretical perspectives, this study examines the role of mothers’ employment and its impacts on children’s participation in a STEM field through three pathways of school achievement, the development of mathematics efficacy and family investment. With the use of data from four nationally representative samples, including HS&B (1980), NELS (1988), ELS (2002), and HSLS (2009), the results suggest that the effect of mothers’ employment on students’ STEM participation was present only in the HSLS09 cohort. The effect of mothers’ paid work on a STEM major was mediated through school achievement and mathematics efficacy. The complexity of mothers’ job may play an enhancement role in supporting children’s decision in a STEM field through mathematics efficacy.