The extreme weather conditions negatively affect the traffic flow performance, and the change of traffic systems has significant impacts on the air pollutant emission. This study identifies the correlation between rainfall, traffic volume, travel speed and air pollution concentration (NO2 and PM10) in Seoul. We employed a path analysis using rainfall data from Korea Meteorological Administration and Seoul’s air quality and traffic monitoring data in July and August on 2014. It is found that the occurrence of rainfall decreases NO2 and PM10 concentration due to the higher washing effect, while rainfall increases NO2 and PM10 concentration via the changes in traffic volume and traffic speed. The analysis of the rainfall intensity reveals that the rainfall increases NO2 concentration due to the traffic volume increase and the traffic speed reduction if an hourly rainfall is more than 5mm. It is to note that the current model succeeds in identifying the relationship between weather conditions, traffic flow performance and air pollution in a unified and consistent framework, which can be used for better predicting the changes in air pollution concentration.