Currently, work-family conflict of college teachers is a common issue, especially when their children are in the preschool stage, which will directly affect the children's problem behaviors. This study aims to explore the relationship between parental work-family conflict and children's problem behaviors, and the mediating role of parental phubbing and children's problematic media use among Chinese college teachers. A total of 234 college teachers and their preschool children (Mean[subscript age] = 60.29 months) participated in this study. The results indicate that: (1) there is a significant positive correlation between college teachers' work-family conflict and their children's problem behaviors; (2) there is a significant mediating effect of problematic media use between work-family conflict and preschool children's problem behaviors; and (3) Parental phubbing and children's problematic media use play a chain mediating role between work-family conflict and children's problem behaviors. The results reveal the influencing mechanism of work-family conflict on preschool children's problem behaviors.