Unstable temperature stratification conditions have a considerable influence on pollutant diffusion inside street canyons. In this study, we tried to model the air flow and particle dispersion in street canyons under unsteady thermal environment. The sinusoidal variation was used to model the atmosphere temperature on the basis of the solar radiation cycle that occurs over a day. The two-dimensional model of step-up building layouts was applied as the research object and an RNG turbulence model was applied to study the dynamic characteristics of instantaneous airflow, the dimensionless air exchange rate (ACH) and turbulent kinetic energy (TKE) in the different canyons. A series of numerical simulations were performed for different Richardson numbers (Ri). The results demonstrated that the stream function within the street canyons exhibited a periodic shift over a day, and the flow morphology gradually evolved from paralleled bilateral vortexes into a row of vortexes, particularly when the ground temperature increased. Moreover, the local PM concentrations at different times were obtained, and they were affected by the flow field patterns. The total PM mass in the street canyon decreased as the air velocity increased. Furthermore, the dimensionless ACH and TKE exhibit a noticeable fluctuation with time at higher Ri and stronger buoyancy. As the Ri decreases, the enhanced forced convection causes the ACH and TKE to remain constant over time. From these results, inhabitants should be advised to adopt preventative measures aimed at the PM pollution according to the time and location where they live.