Abstract Outdoor tobacco smoke (OTS) is concerned due to potential health effects. An assessment method of OTS exposure is needed to determine effects of OTS and validate outdoor smoking policies. The objective of this study was to develop a new method to assess OTS exposure. This study was conducted at 100 bus stops including 50 centerline bus stops and 50 roadside bus stops in Seoul, Korea. Using real-time aerosol monitor, PM2.5 was measured for 30 min at each bus stop in two seasons. ‘Peak analysis’ method was developed to assess short term PM2.5 exposure by OTS. The 30-min average PM2.5 exposure at each bus stop was associated with season and bus stop location but not smoking activity. The PM2.5 peak occurrence rate by the peak analysis method was significantly associated with season, bus stop location, observed smoking occurrence, and the number of buses servicing a route. The PM2.5 peak concentration was significantly associated with season, smoking occurrence, and the number of buses servicing a route. When a smoker was standing still at the bus stop, magnitude of peak concentrations were significantly higher than when the smoker walking-through the bus stop. People were exposed to high short-term PM2.5 peak levels at bus stops, and the magnitude of peak concentrations were highest when a smoker was located close to the monitor. The magnitude of peak concentration was a good indicator helped distinguish nearby OTS exposure. Further research using ‘peak analysis’ is needed to measure smoking-related exposure to PM2.5 in other outdoor locations.