Childhood is an important period of individual psychological development, and parents’ company and parenting styles are highly significant to children’s personality cultivation and mental health. With the advancement of China’s modernization and urbanization, left-behind children without their parents’ company have become a growing concern. Compared with children raised by their parents, left-behind children are more likely to show social maladaptation and mental health problems. This study explored the mediating effects of left-behind children’s dual mode of self-control between caregivers’ parenting styles and emotional and behavioral problems (EBPs). In this study, 469 left-behind children in senior classes of primary schools were investigated by adopting the caregivers’ parenting styles questionnaire of left-behind children, the dual-mode of self-control scale and the strengths and difficulties questionnaire. This study found that (1) the protective and risk factors for caregivers’ parenting styles not only directly affected EBP, but also affected it through the mediating effect of the dual-mode of self-control, and (2) the mediating effect of the impulsive system was significantly greater than that of the control system. This study confirmed that caregivers’ parenting styles had an important impact on left-behind children’s psychological growth: positive parenting styles not only directly reduced the risk of EBP, but also indirectly improved left-behind children’s mental health by promoting their level of self-control; negative parenting styles directly increased the risk of EBP and indirectly affected left-behind children’s mental problems by enhancing their level of impulsiveness. These findings provide an important basis for reducing the risk of mental health problems and cultivating good personality qualities of left-behind children.