Abstract Urban heat island (UHI) can considerably affect the thermal quality of the urban environment, especially within urban canyons, that have typically low sky view factor and limited surface heat re-emission capability. A huge research effort has been registered to develop mitigation solutions for UHI, such as cool materials and greenery. Nevertheless, it is not always possible to apply such strategies in historical urban environments due to constrains for the preservation of their cultural value that do not allow to modify the exterior architectural appearance of heritage buildings. In this scenario, the present paper deals with the analysis of the potential of innovative cool materials characterized by the same appearance of historical ones in mitigating the UHI occurring in the context of a historical urban canyon located in central Italy selected as pilot case study. To this purpose, a preliminary experimental characterization of such innovative highly reflective materials has been performed. Afterwards, an experimental continuous monitoring campaign of the main outdoor microclimate parameters and a numerical modelling of the canyon have been carried out to evaluate the local mitigation capability of such materials when applied over the vertical and horizontal surfaces of the historical canyon. The results show the huge potential of the proposed innovative cool materials in mitigating the local microclimate of the historical urban canyon. In fact, a MOCI reduction up to 0.15 and 0.30 is detected by applying cool red envelope materials and cool red envelope materials plus cool grey paving materials, respectively, on the canyon surfaces.