This study examined the association of pharmacological treatments and academic achievement among children with attention-deficit/hyperactivity disorder (ADHD). Results examining the association of pharmacological treatments and academic achievement among children with ADHD are mixed. Our objective was to examine this association using structural equation modeling (SEM) techniques, which may be considered more sophisticated and advanced over traditional regression techniques. To achieve the purpose, we employed a sample of children with ADHD derived from the Early Childhood Longitudinal Study-Kindergarten (ECLS-K) data. The ECLS-K provides a large, community-based, nationally representative sample of children to examine across time with respect to academic achievement outcomes. The present study reveals a statistically nonsignificant association between pharmacological treatment and academic achievement among children with ADHD. These results derived from a large, community-based, nationally representative sample, using SEM techniques, may be considered highly generalizable.