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The expansion of publicly funded early childhood care and education (ECCE) programs may yield benefits to families beyond direct effects on children’s educational and social outcomes. Access to free or subsidized ECCE provides families with childcare for young children, freeing up time for primary caregivers, most often mothers, to engage in the labor market or invest in their own human capital. The largest federally funded ECCE program, Head Start, provides free, educational opportunities for children and care options for families living in poverty. This paper leverages the variable timing of the rollout of full-day Head Start in the 1990s to evaluate the effect of expanding opportunities for free childcare on the employment and educational enrollments of low-income mothers. I do not find an effect of full-day Head Start expansion on the probability low-income mothers engage in the labor market or enroll in school. However, among single mothers, I find the expansion of full-day Head Start predicts increased probability of employment across most specifications. Results inform our understanding of childcare’s role in mother’s investments in the labor market and human capital and inform policies aimed at supporting families living in poverty.