Using data ("n" = 3,790 with 2,119 in the 3-year-old cohort and 1,671 in the 4-year-old cohort) from 353 Head Start centers in the Head Start Impact Study, the only large-scale randomized experiment in Head Start history, this article examined the impact of Head Start on children's cognitive and parent-reported social-behavioral outcomes through first grade contingent on the child care arrangements used by children who were randomly assigned to the control group (i.e., parental care, relative/nonrelative care, another Head Start program, or other center-based care). A principal score matching approach was adopted to identify children assigned to Head Start who were similar to children in the control group with a specific care arrangement. Overall, the results showed that the effects of Head Start varied substantially contingent on the alternative child care arrangements. Compared with children in parental care and relative/nonrelative care, Head Start participants generally had better cognitive and parent-reported behavioral development, with some benefits of Head Start persisting through first grade; in contrast, few differences were found between Head Start and other center-based care. The results have implications regarding the children for whom Head Start is most beneficial as well as how well Head Start compares with other center-based programs.