Computational fluid dynamics simulations were performed to investigate flow and pollutant dispersion in a 2D street canyon of aspect ratio H/W = 1. Different from other works, the combination of the presence of viaduct and indoor–outdoor temperature differences ΔT is investigated for different approaching wind velocities. For larger wind velocity (2 m/s, Froude number Fr~3.06–12.24) the typical clockwise vortex leads to higher concentrations of both gas and small particles at the leeward side of the street and in the leeward-side rooms; the vortex is enhanced under large ΔT (20 K) improving the dispersion of pollutants. For smaller velocity (0.5 m/s, Fr~0.19–0.77) the appearance of an anti-clockwise vortex leads to a strong accumulation of gas and particles at the windward side and in the windward-side rooms under low ΔT (5 K); increasing the ΔT raises the dispersion of pollutants with consequent lower concentrations in the rooms (up to an average of 67% with respect to the isothermal case for gaseous pollutants), but accumulation close to the ground level at both windward-side and leeward-side rooms. In the presence of viaduct, together with the main vortex above the viaduct which causes concentrations increasing from low-level to high-level leeward-side rooms, two vortices are generated below it. Still ΔT = 20 K improves the dispersion of pollutants, leading up to a maximum of about 30% lower gaseous concentrations in the rooms. In general, lower concentrations of gas and particles are found for larger velocity, indicating that the mechanical turbulence dominates over the buoyancy effects, which become crucial for smaller velocity. This study confirms previous findings that viaducts may improve pollutant dispersion under large velocity if only one viaduct-level pollutant source exists and indoor–outdoor ΔT conditions can mitigate street air pollution.