Data from the National Longitudinal Survey of Youth are used to explore the educational achievement of youths who lived away from both biological parents for at least four months during childhood. The study focuses on those who spent some time in substitute care (in foster family care, living with relatives, or in institutions), those who left home to be on their own before age 17, and children who were adopted by a couple before age 2. Educational achievement is measured by high school completion, college completion, and highest grade completed by age 25. The 5 to 10 percent of youths in this study who experience surrogate forms of family care on average have lower educational achievement than those who grew up with both biological parents. The educational level of the parents appears to play an important role, and may explain a significant portion of this discrepancy. This study cannot sort out whether the differences in educational achievement reflect the types of youths who enter surrogate forms of care, the reasons for transitions, or the actual substitute care experiences. Its contribution is that it adds analysis of a nationally representative sample of youth to a very thin body of literature on substitute care. (author abstract)