Numerous researchers all over the world have spent efforts in assessing the local microclimate of the built environment on different scales (e.g., from a city scale to a district and neighborhood scale) both through monitoring campaigns and validated and calibrated microclimatic models for numerical simulations. Advanced microclimate analysis is of fundamental importance especially to predict, understand, and quantify the impact that the implementation of urban mitigation strategies can produce in the built environment. The impact can be measured in terms of the main environmental parameter's variation (e.g., air temperature, surface temperature, relative humidity, wind speed and direction) and can produce effects on outdoor thermal comfort, energy consumption, health, social and economic factors. With the growing concern about the global challenge of climate change, linked with the increased frequency of local extreme heat events, the urban heat island phenomenon, and their deriving impacts on the built environment and people, a great attention has been drawn into the design, optimization, and implementation of active and passive mitigation strategies able to reduce the outdoor thermal discomfort for pedestrians and the urban overheating during the hot season. In addition to the more common cooling strategies for the outdoor spaces (e.g., cool materials, thermochromic material, retro-reflective materials, shading devices, vegetation and trees among the passive strategies), there are effective daytime radiative coolers that can be implemented in the built environment, for example to improve the outdoor thermal comfort for pedestrians. Impressive improvements have been achieved in the development of technologies for daytime radiative cooling. Some of those technologies can reduce their surface temperature much below the air temperature in their proximity (about 10 C less on average, and up to approx. 40 C less depending on the specific used technology). Materials and systems presenting daytime radiative cooling potential are characterized by high solar reflectivity (especially in the range 0.25-2.8 mm) and selective thermal emittance (e.g., high emittance in the atmospheric windows 8-13 mm and close to zero elsewhere). Nowadays, existing microclimate simulation models (such as ENVI-met, PALM, CitySim, SOLENE-microclimate and more) do not consider the possibility to model materials characterized by selective thermal emissivity, such as the radiative cooling materials. To cover this important gap, this study aims to develop a methodology and a numerical tool able to simulate the thermal-energy behavior of urban surfaces characterized by a daytime radiative cooling potential in the context of the microclimate analysis.