Based on theoretical premises of ecological systems theory and the compensatory hypothesis, a subset of data from the Family Life Project (N = 773), a population-based study of rural families with low incomes, were used to test for associations between maternal literacy in infancy and children’s academic outcomes and teacher-reported problem behaviors in kindergarten. A second aim tested whether increased time in child care averaged from 6 to 36 months moderated such relations. Results indicated that maternal literacy was significantly positively related to academic outcomes (ES = 0.17–0.23) and significantly negatively related to children’s problem behaviors (ES = −0.15) in kindergarten. Child care hours were not significantly related to any outcome. Significant interactions were found between maternal literacy and hours in child care on both children’s academic skills and problem behaviors. Specifically, for mothers with lower literacy levels, significant dose-response relationships were detected between increased time in child care and children’s higher academic scores and reduced problem behaviors (ES = 0.07–0.09). Implications for maternal literacy and child care access among rural families are discussed.