Ongoing climate change is manifesting in the expansion of the urban heat island (UHI) effect. This paper evaluates the microclimate benefits of cool pavements and green infrastructures in a historical square in Rome, Italy. The ENVI-Met software enabled us to conduct a microclimatic analysis of the examined square in July 2021, through a comparison of the thermal performances of the current asphalt and sampietrini pavement (AS) with three alternatives. The proposed options are to change the existing layout to include: light concrete slabs and green furniture consisting of 5 m high trees (LC+G1), a perimeter hedge with 5 m high trees (LC+G2), and a perimeter hedge with 15 m high trees (LC+G3). The effects of the road pavements as passive countermeasures to the UHI effect are investigated in terms of air temperature (AT), mean radiant temperature (MRT), and predicted mean vote (PMV). The results show that the existing asphalt pavement is the worst option, while the cool pavement integrated with vegetation is greatly beneficial to human thermal comfort. Compared to the current layout, LC+G3 is the best scenario, because it implies an AT reduction higher than 3 °C, a MRT reduction equal to 50%, and a maximum PMV value equal to 2.2.