Objective: To explore the relationship between peer social network positions and smoking experimentation among Chinese adolescents. Methods: Self-administered questionnaires were administered to 1040 adolescents in grades 6, 8, and 10. Paired-friendship linkages were used to assign participants into 3 mutually exclusive social network positions. Results: Overall isolates were more likely to have experimented with cigarettes than were group members or liaisons. However, among male 10th graders, more group members or liaisons had smoked than isolates. Conclusion: Smoking experimentation differs by social position, particularly among older adolescents. The association of social position with smoking experimentation could not be explained completely by traditional peer-related variables.