A longitudinal, prospective design was used to examine the roles of peer rejection in middle childhood and antisocial peer involvement in early adolescence in the development of adolescent externalizing behavior problems. Both early starter and late starter pathways were considered. Classroom sociometric interviews from ages 6 through 9 years, adolescent reports of peers' behavior at age 13 years, and parent, teacher, and adolescent self-reports of externalizing behavior problems from age 5 through 14 years were available for 400 adolescents. Results indicate that experiencing peer rejection in elementary school and greater involvement with antisocial peers in early adolescence are correlated but that these peer relationship experiences may represent two different pathways to adolescent externalizing behavior problems. Peer rejection experiences, but not involvement with antisocial peers, predict later externalizing behavior problems when controlling for stability in externalizing behavior. Externalizing problems were most common when rejection was experienced repeatedly. Early externalizing problems did not appear to moderate the relation between peer rejection and later problem behavior. Discussion highlights multiple pathways connecting externalizing behavior problems from early childhood through adolescence with peer relationship experiences in middle childhood and early adolescence.