Many students in Korea begin to use tobacco and develop a regular smoking habit before they reach adulthood. Yet, little is known about various signs contributing to the transition of the student smoking behaviors. This study used a national sample to explore and compare risk factors for smoking behaviors. Three types of smoking behaviors were defined: never smoking (in their lifetime), history of experimental smoking (ever tried but not within the last 30 days), and current smoking (at least 1 day during the last 30 days). Risk factors for experimentally starting and not continuing smoking were identified as gender, perceived health status, and friend-related stress. School type, academic performance, alcohol use, perception of harm of smoking, and close friends’ smoking increased the risk of progressing from never smoking to the history of experimental smoking and current smoking. Our findings may be valuable in school health care settings in planning cessation programs.