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Previous studies have found that mothers’ use of a negative parenting style is a risk factor for adolescent deviant peer affiliation, but it is not clear if mother rejection and overprotection affect deviant peer affiliation similarly, or if the mechanism is different for these two parenting styles. Through a survey of 856 high school students in eastern China we measured mothers’ rejection or overprotection and students’ violence exposure, teacher–student relationship, and deviant peer affiliation. The results showed that in the link between mother’s rejection and adolescents’ deviant peer affiliation, the mediating effect of both violence exposure and the teacher–student relationship was significant, and the mediating effect of the teacher–student relationship was significantly greater than that of violence exposure. In the link between mother’s overprotection and adolescent deviant peer affiliation, the mediating role of violence exposure was significant. These results show that mothers’ rejection and overprotection each affect adolescent deviant peer affiliation via different mechanisms and suggest that targeted interventions in adolescents’ deviant peer affiliation should distinguish between rejection and overprotection.