This article presents the results of the thermal survey of the capital of Bulgaria (Sofia) carried out in August 2019, with the application of an unmanned aerial system (UAS). The study is based on the concept of local climate zones (LCZs), taking into account the influence of the features of land use/land cover and urban morphology on the urban climate. The basic spatial units used in the study are presented in the form of a regular grid consisting of 3299 cells with sides of 250 ´ 250 m. A total of 13 types of LCZs were identified, of which LCZs 6, 5, 8, 4, D, and A form the largest share. In the thermal imaging of the surface, a stratified sampling scheme was applied, which allowed us to select 74 cells, which are interpreted as representative of all cells belonging to the corresponding LCZ in the urban space. The performed statistical analysis of the thermal data allowed us to identify both the most thermally loaded zones (LCZs 9, 4, and 5) and the cells forming Urban Cool Islands (mainly in LCZs D and C). The average surface temperature in Sofia during the study period (in the time interval between 8:00 PM and 10:00 PM) was estimated at 20.9 °C, and between the different zones it varied in the range 17.2–25.1 °C. The highest maximum values of LST (27.9–30.6 °C) were registered in LCZ 4 and LCZ 5. The relation between the spatial structure of the urban thermal patterns and urban surface characteristics was also analyzed. Regression analysis confirmed the hypothesis that as the proportion of green areas increases, surface temperatures decrease, and, vice versa, as the proportion of built-up and impermeable areas increases, surface temperatures increase. A heat load map (via applying a z-transformation to standardize the temperature values), a map of the average surface temperature, and a map of the average intensity of the heat island on the surface were generated in the GIS environment. The results of the study adequately reflect the complex spatial model of the studied phenomenon, which gives grounds to conclude that the research approach used is applicable to similar studies in other cities.