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Peer-assisted learning is widely deployed in Nigerian agricultural education programmes, yet its psychological mechanism, particularly its effects on academic self-concept and achievement goal orientation, remains empirically underexplored. This study determined the influence of peer-assisted learning and self-concept on achievement goal orientation among 300-level and 400-level agricultural science undergraduate students in Southwest Universities of Nigeria. A correlational survey design was employed with 308 students from five universities across Lagos, Ondo, and Osun States. Four validated instruments measured peer-assisted learning quality, agricultural science academic self-concept, mastery goal orientation, and performance goal orientation. Pearson correlation, multiple regression, and MANOVA were employed. Peer-assisted learning quality correlated significantly with academic self-concept, r(306) = .64, p < .001, and with mastery goal orientation, r(306) = .57, p < .001. Academic self-concept significantly mediated the relationship between PAL and mastery goal orientation (indirect effect = 0.29, 95% CI [0.21, 0.38]). Gender and prior achievement significantly moderated PAL effects on self-concept. The full model explained 58.2% of the variance in mastery goal orientation. Institutionalizing structured peer-assisted learning with explicit self-concept building components is recommended for Southwest Nigerian agricultural education programmes.