The family environments children live in have profound effects on the skills, resources, and attitudes those children bring to school. Researchers studying family structure have found that children who live with two married, opposite-sex, biological parents, on average, have better educational outcomes than children living in alternate family structures, perhaps due to higher resources, lower stressors, or different selectivity patterns. Socioeconomic stratification plays a major role in family structure, with low-income families seeing more instability. We argue that the impact of family structure is attenuated by transitions in and out of family structures that may decrease a specific resource important to child academic outcomes: parental involvement. This may contribute to increased academic differences already noted across class gaps. Using waves 1 to 6 of the Growing Up in Australia: Longitudinal Study of Australian Children (LSAC) data, we examine the relationship of family stability and transitions from birth to age 10/11 years on parental involvement and educational outcomes, adjusted for resource, stressor, and selectivity covariates. We find that changes in parental involvement are only apparent for families that experience both a transition and single parenting, and that these differences in parental involvement impact academic outcomes.