Previous researchers calculated air change rate per hour (ACH) in the urban canopy layers (UCL) by integrating the normal component of air mean velocity (convection) and fluctuation velocity (turbulent diffusions) across UCL boundaries. However they are usually greater than the actual ACH induced by flow rates flushing UCL and never returning again. As a novelty, this paper aims to verify the exponential concentration decay history occurring in UCL models and applies the concentration decay method to assess the actual UCL ACH and predict the urban age of air at various points. Computational fluid dynamic (CFD) simulations with the standard k-ε models are successfully validated by wind tunnel data. The typical street-scale UCL models are studied under neutral atmospheric conditions. Larger urban size attains smaller ACH. For square overall urban form (Lx = Ly = 390 m), the parallel wind (θ = 0°) attains greater ACH than non-parallel wind (θ = 15°, 30°, 45°), but it experiences smaller ACH than the rectangular urban form (Lx = 570 m, Ly = 270 m) under most wind directions (θ = 30° to 90°). Open space increases ACH more effectively under oblique wind (θ = 15°, 30°, 45°) than parallel wind. Although further investigations are still required, this paper provides an effective approach to quantify the actual ACH in urban-like geometries.