Previous studies have revealed morphologic alterations in patients with major depressive disorder (MDD) with experiences of childhood trauma. However, the underlying neural mechanisms remain largely unknown. This study aims to explore the brain structural changes and their possible mediation role in the relationship between childhood maltreatment and psychological resilience in drug-naïve adolescents with first-episode MDD. A total of 57 adolescents with first-episode MDD and 36 healthy controls (HCs) completed the T1-weighted magnetic resonance imaging scan. The adverse childhood experiences and current psychological resilience were assessed using the Childhood Trauma Questionnaire-Short Form and the Connor Davidson Resilience Scale, respectively. The voxel-based morphometry approach was applied to examine changes in the gray matter volume (GMV). Compared with the HCs, adolescents with MDD had significantly reduced GMV volumes in the left fusiform gyrus, right orbitofrontal gyrus, right superior temporal gyrus, right calcarine cortex, right middle frontal gyrus, left angular gyrus, right precuneus, right posterior cingulate gyrus, and right posterior central gyrus, as well as significantly increased GMV volumes in the left lenticular putamen and right lenticular pallidum. The GMV of the right calcarine cortex was found to be negatively correlated with the severity of emotional abuse and positively correlated with the level of psychological resilience. Moreover, the GMV of the right calcarine cortex might partially mediate the relationship between childhood maltreatment and psychological resilience. The present study provided further evidence for structural impairments in adolescents with MDD. Our findings also confirmed the important role of depression-related GMV changes in childhood growth experiences and psychological resilience characteristics during adolescent brain maturation.