Social cognitive complexity was a concept reflecting individual differences on social cognitive structure. However, as a hot research topic in the field of social cognitive psychology, few studies have concerned the relationship between social cognitive complexity and peer interaction. Based on a sample of 234 Chinese adolescents from 7th through 11th grades, the present study firstly investigated the relationship between social cognitive complexity and peer interaction, then discussed their relation path using structural equation model (SEM) fatherly. The results showed that (1) there were significant correlation among social cognitive complexity and peer acceptance, peer rejection, interpersonal competence, social preference. The adolescent with higher social cognitive complexity has higher interpersonal competence and academic achievement, received more peer acceptance while less peer rejection. (2) interpersonal competence and academic achievement were mediator variables between social cognitive complexity and peer popularity, social cognitive complexity could affect an individuals’ popularity in peer group by influencing his/her interpersonal skills and academic achievement.