Acceptance and rejection by parents and peers play an important role in pre-adolescents' educational outcomes. Prior research focused on either parents or peers, did not encompass effects into adulthood, or considered either acceptance or rejection. This study investigated the relation between parental and peer acceptance and rejection, and their interplay, in pre-adolescence and educational attainment in early adulthood. A sample of 2229 pre-adolescents (M-age T1 = 11.11, SD = 0.56; 50.7% girls) was followed to early adulthood (M-age T5 = 22.29, SD = 0.65). Ordinal logistic regression showed that pre-adolescents' perceived parental acceptance was positively related to educational attainment in early adulthood, whereas peer rejection was negatively related, even when WISC score and socioeconomic status were considered. No interaction effects were found, revealing no "dual-hit effect" of being rejected by parents and peers, no "dual-miss effect" of being accepted by parents and peers, and no effects of acceptance in one context (i.e., parents or peers) buffering the negative effect of rejection in the other context. The findings underscore unique and long-term links of parental acceptance and peer rejection with early adults' educational attainment, underlining the importance of not only peers but also parents in adolescence. These insights can be used in promoting long-term educational outcomes through relationships with parents and peers.