We examined trajectories of academic and social functioning in children with attention-deficit/hyperactivity disorder (ADHD) to identify those who might be at risk for especially severe levels of academic and social impairment over time. We estimated a series of growth mixture models using data from two subsamples of children participating in the NIMH Collaborative Multisite Multimodal Treatment Study of Children with ADHD (MTA) including those with at least baseline and 96-month data for reading and mathematics achievement (n = 392; 77.3% male; M age = 7.7; SD = 0.8) or social skills ratings from teachers (n = 259; 74.9% male; M age = 7.6; SD = 0.8). We compared latent trajectories for children with ADHD to mean observed trajectories obtained from a local normative (i.e., non-ADHD) comparison group (n = 289; 80.6% male; M age = 9.9; SD = 1.1). Results indicated six latent trajectory classes for reading and mathematics and four classes for teacher social skills ratings. There was not only a relationship between trajectories of inattention symptoms and academic impairment, but also a similarly strong association between trajectory classes of hyperactive-impulsive symptoms and achievement. Trajectory class membership correlated with socio-demographic and diagnostic characteristics, inattention and hyperactive-impulsive symptom trajectories, externalizing behavior in school, and treatment receipt and dosage. Although children with ADHD display substantial heterogeneity in their reading, math, and social skills growth trajectories, those with behavioral and socio-demographic disadvantages are especially likely to display severe levels of academic and social impairment over time. Evidence-based early screening and intervention that directly address academic and social impairments in elementary school-aged children with ADHD are warranted. The ClinicalTrials.gov identifier is NCT00000388.