Urban heat islands (UHI) are one of the unequivocal effects of the ongoing process of climate change: anthropized areas suffer extreme heat events that affect the human perception of comfort. This study investigated the effects of road pavements as a passive countermeasure by comparing the air temperature (AT) and the predicted mean vote (PMV) for different surface materials used to pave a historical square in Rome, Italy. The software ENVI-met has been used to compare, for the whole year 2021, the performances of the existing asphalt pavement with five alternative solutions composed of light concrete, bricks, stone, wood, and grass. This paper proposed a new methodology to summarize the multi-dimensional results over both temporal and spatial domains. The results of the simulations in the evening of the hottest month showed the existing asphalt pavement gives the worst performance, while the light concrete blocks and the grass pavement ensure the coolest solutions in terms of AT (the average AT is 32 °C for the asphalt pavement and 30 °C for the modular one) and PMV (the maximum PMV value is 4.6 for the asphalt pavement and 4.4 for the modular and grass ones).