Materials for urban pavements and building coatings have a direct impact on urban thermal environment: low-reflective and highly absorptive materials, in fact, could contribute to the exacerbation of the Urban Heat Island (UHI) phenomenon, which negatively affects building energy consumptions and indoor and outdoor thermal comfort. These effects could be worsened especially in Urban Heat Canyon configurations, where the inter-building effect becomes more relevant. As regards UHI mitigation strategies, high-reflective (HR) and retro- reflective (RR) materials have been studied for their application as urban coatings, in order to provide a cooling effect inside urban canyons. In this framework, this study aims at comparing the albedo performance of HR and RR materials applied on a small scale urban canyon facility. To this aim, an in-field experimental campaign was conducted in two days during summer 2020. Different canyon coating combinations and height/width (H/W) ratios were investigated and compared in terms of albedo. Results show that an albedo worsening occurs when the RR coating was applied to the canyon’s surfaces, because of the lower global reflectance of the RR with respect to the HR. Nevertheless, the application of RR coating on walls, coupled with HR paint on pavement, lead to higher albedo values of up to 4.7%, with respect to the opposite mixed coating combination. Future developments may concern the investigation of the optimum design of a glass bead RR material for building application, by studying the correlation between its optical capabilities and the dimensions and density of the glass beads.