The comprehensive theory model of problem behaviors proposed that expectations are important factors affecting adolescent problem behaviors. The purpose of this study is to explore the association between educational expectations (in this study, this includes parental educational expectations and adolescent selfeducational expectations) and problem behaviors based on the framework of the CTMPB to provide empirical support for the prevention and intervention of adolescent problem behaviors. This study used cross-sectional data from the 2014–2015 academic year of the China Education Panel Survey (CEPS) conducted by the China survey and data center at the Renmin University of China. A nationwide representative sample of 9936 junior high school students was selected. Among them, 4870 (52.2%) were female, and the average age was 14.52 years (SD = 0.67 years). The results revealed that adolescent selfeducational expectations and deviant peer affiliations played a contributory mediating role in the association between parental educational expectations and adolescent problem behaviors. Both parental educational expectations and adolescent selfeducational expectations are protective factors against adolescent problem behaviors, and enhancing the two factors can decrease the likelihood of adolescent engagement in problem behaviors. In addition, deviant peer affiliations are risk factors for adolescent problem behaviors and represent a mediating factor between educational expectations and adolescent problem behaviors. However, this study was only based on cross-sectional data, requiring further support by longitudinal or experimental studies.