This study presents a comprehensive modeling approach for simulating the spatiotemporal distribution of urban air temperatures with a modeling system that includes the Weather Research and Forecasting (WRF) model and the Single-Layer Urban Canopy Model (SLUCM) with a modified treatment of the impervious surface temperature. The model was applied to simulate a 3-day summer heat wave event over the city of Athens, Greece. The simulation, using default SLUCM parameters, is capable of capturing the observed diurnal variation of urban temperatures and the Urban Heat Island (UHI) in the greater Athens Area (GAA), albeit with systematic biases that are prominent during nighttime hours. These biases are particularly evident over low-intensity residential areas, and they are associated with the surface and urban canopy properties representing the urban environment. A series of sensitivity simulations unravels the importance of the sub-grid urban fraction parameter, surface albedo, and street canyon geometry in the overall causation and development of the UHI effect. The sensitivities are then used to determine optimal values of the street canyon geometry, which reproduces the observed temperatures throughout the simulation domain. The optimal parameters, apart from considerably improving model performance (reductions in mean temperature bias from 0.30 °C to 1.58 °C), are also consistent with actual city building characteristics – which gives confidence that the model set-up is robust, and can be used to study the UHI in the GAA in the anticipated warmer conditions in the future.