The present study aims to estimate the wind ventilation performance for pedestrian level domains from the air quality point of view. Three typical models of a dense urban area were considered and numerically simulated in order to examine the effects of the geometry of such models on wind flow characteristics, which in turn affect the air quality, within the pedestrian domain of a street canyon located within this area. The calculated flow fields were employed to estimate the exceedance probabilities within the study domain using a new approach: air exchange rate within the domain. The study has been applied to nine cities in Japan: Tokyo, Osaka, Sapporo, Niigata, Fukuoka, Nagoya, Sendai, Yokohama, and Kyoto, based on their mean wind velocity data. The results demonstrated that the exceedance probability analysis of the pedestrian wind environment could be a valuable tool during the design stage of inhabited areas for the evaluation of pollutant-removal efficiency by the applied wind. Also, the calculated probabilities demonstrated substantial dependence on both the geometry of building arrays and the wind conditions of the nine cities.