The diurnal variation of NOx and O3 exchange between a street canyon and the overlying air in two dimensions is investigated to understand reactive pollutant removal and entrainment across the roof level of the street canyon. The computational fluid dynamics (CFD) model used in this study is a Reynolds-averaged Navier-Stokes equations (RANS) model and includes the urban surface and radiation processes and the comprehensive chemical processes. The CFD model is used for the one-day simulation in which the easterly ambient wind blows perpendicular to the north-south oriented street canyon with a canyon aspect ratio of 1. In the morning when the surface temperature of the downwind building wall is higher than that of the upwind building wall, two counter-rotating vortices appear in the street canyon (flow regime II). In the afternoon when the surface temperature of the upwind building wall is higher than that of the downwind building wall, an intensified primary vortex appears in the street canyon (flow regime I). The NOx and O3 exchange is generally active in the region close to the building wall with the higher temperature regardless of flow regime. The NOx and O3 exchange by turbulent flow is dominant in flow regime II, whereas the NOx and O3 exchange by mean flow becomes comparable to that by turbulent flow in a certain period of flow regime I. The NOx and O3 exchange velocities are similar to each other in the early morning, whereas these are significantly different from each other around noon and in the afternoon. This behavior indicates that the exchange velocity is dependent on flow regime. In addition, the diurnal variability of O3 exchange velocity is found to be dependent on photochemistry rather than dry deposition in the street canyon. This study suggests that photochemistry as well as flow in a street canyon is needed to be taken into account when exchange velocities for reactive pollutants are estimated.