In a context of urban warming, the effects of trees on outdoor thermal stress are important even during the increasingly hot autumn season. This study examines the effects of a deciduous tree species (Tilia x europaea L) on surface temperature over different ground materials and in turn on human thermal comfort, with a particular focus on tree shade variation due to leaf fall. Grass, asphalt, and gravel-covered ground surfaces, both sun-exposed and under the Tilia, were monitored in Florence, Italy, during the summer (2014) and autumn (2017) seasons. The Index of Thermal Stress (ITS) was used to gauge the micrometeorological effects of the changing tree canopy, with tree defoliation quantified by the Plant Area Index. On clear summer days, thermal discomfort was especially pronounced over exposed asphalt, and even more intense above exposed gravel due to its higher reflectivity-while shaded surfaces showed large reductions in thermal stress. Even though incoming solar radiation decreases over the course of the fall season, the direct radiation under the gradually defoliating tree canopy actually increases. Due to this diminished shading effect, the differences in surface temperature between exposed and shaded asphalt shrink dramatically from about 20 to 3 °C. However, since ambient conditions become milder as the season progresses, the Tilia demonstrated a double benefit in terms of ITS: providing thermal comfort under its full canopy at the beginning of autumn and maintaining comfort even as its canopy thins out. At the same time, tree species with earlier defoliation may be unable to replicate such benefits.