Background: Pubertal timing refers to the timing of an individual regarding pubertal sexual maturation, both physiologically and psychologically. Existing research shows that pubertal timing is associated with behavioral problems. This study investigated the role of parenting style in the relationship between pubertal timing and Chinese adolescents’ smoking behavior. Methods: The study examined the association of pubertal timing, parenting style and adolescents’ smoking behavior, using the Pubertal Development Scale (Chinese version), Simplified Parenting Style Scale-Chinese version, and three items related to adolescents’ smoking situation. Participants were 1391 Chinese adolescents aged 11–16 years old (53.41% boys). Hierarchical linear regression analyses assessed the moderating role of parenting style on the association between pubertal timing and adolescent smoking behavior. Results: The results indicated that parenting style moderates the relationship between pubertal timing and adolescent smoking behavior. For male adolescents, father rejection moderated the relationship between early pubertal timing and smoking behavior. For female adolescents, father rejection, father emotional warmth, and mother emotional warmth moderated the relationship between pubertal timing and smoking behavior. Conclusions: Findings from the study highlight the importance of parenting style, which may influence the negative outcomes associated with early pubertal timing and can help improve interventions aimed at reducing these negative outcomes.