This study used data from Early Childhood Longitudinal Study -- Birth Cohort (ECLS-B) and examined the relations between children's Head Start exposure and their early academic skills (i.e., language, literacy, and math skills) in the United States. Two groups of children who shared similar socio-economic status and disability status but received different types of early child care services (i.e., Head Start programs vs. any other arrangement) were identified from the ECLS-B dataset. Multiple regression analyses identified unique relations between the length of time that children experienced Head Start programs and their early academic skills after controlling for child and family characteristics. The results showed that children's Head Start enrollment duration was a significant, positive predictor of their early receptive language, literacy, and math skills. No significant relation was found between Head Start enrollment and children's expressive language skills. Limitations of the study and suggestions for future research were discussed.