Previous studies uncovered that perceived parental monitoring, personality, and self-control were three important external and internal factors that influenced adolescents’ online deviant behaviors. However, as the dark side of personality, the Dark triad, which implies a disagreeable disposition, lack of humility, belief of being able to predict future outcomes and an opportunistic life strategy, has rarely been used to explore its relationship with online deviant behaviors. Based on problem behavior theory, general aggression model, and models of risk factors and protective factors on problem/deviant behaviors, the current study investigated the relationship among perceived parental monitoring, the Dark Triad, and self-control on online deviant behaviors. A total of 1921 middle and high school students (aged 11–18 years) from China reported their online deviant behaviors (cyberbullying behavior, Internet rumors, deception on the Internet, and cyber obscenity/pornography), perceived parental monitoring, and the Dark Triad as well as the self-control level of individuals. The results of the Pearson correlation showed there were significant correlations among perceived parental monitoring, the Dark Triad, and self-control on online deviant behaviors. The results of the structural equation model (SEM) indicated that the Dark Triad partially mediated the relationship between perceived parental monitoring and online deviant behaviors. Self-control moderated the mediation effect of the Dark Triad. Specifically, self-control weakened the positive relationship between the Dark Triad and online deviant behaviors, and increased the negative relationship between perceived parental monitoring and online deviant behaviors. Our findings expand the applicable environment of the Dark Triad and emphasize its association with online deviant behaviors. Attention should be paid to the interaction of internal traits (e.g., personality and self-control) and explicit family environment (e.g., perceived parental monitoring) in online deviant behavior interventions.