Climate-change-related extreme events impact ecosystems, people, economy, and infrastructures, with important consequences on the real estate market as well. This study aims to investigate the variation of residential buildings’ real estate values in a historic Italian city in relation to the summer surface thermal anomaly pattern and urban features surrounding buildings. Open data from remote sensing products and the national database of the Revenue Agency of Italy were used. Real estate values of residential buildings were spatially analyzed in four urban belts, and the association with daytime summer surface hot- and cool-spot zones was studied through odds ratio (OR) statistic. Urban features (impervious area, tree cover, grassland area, and water body) surrounding residential buildings with different real estate values were also analyzed. Considering the whole Florentine municipality, 13.0% of residential buildings fell into hot-spot zones (only 0.6% into cool-spot ones), characterized by very low tree cover surfaces (generally <1%), most of which were in the central belt (37% of all buildings in central belt). Almost 10% of these buildings belonged to the highest market value class revealing a positive association (OR = 1.53) with hot-spot zones. This study provides useful information to plan targeted building interventions to avoid a probable decrease of the value of residential properties in high heat-related risk areas.