Understanding the relationship between land use and land cover and thermal environment has recently become an emerging issue for urban planners and policy makers. We chose Belgrade, as a case study, to present a cost- and time-effective framework for monitoring spatiotemporal changes of green spaces in relation to the land surface temperature (LST). Time series analysis was performed using Landsat 5 TM and Landsat 8 OLI/TIRS imagery from 1991 to 2019 with an approximate 5-year interval (18 images in total). Spectral vegetation indices and supervised land cover classifications were used to examine changes of green spaces. The results showed a fluctuating trend of the normalized difference vegetation index (NDVI) and the normalized difference water index (NDWI). The highest values were recorded in 2019, indicating vegetation recovery in the last decade. A significant positive correlation was determined between the spectral vegetation indices and the amount of precipitation during growing season. The land cover classification showed that the share of vegetated and bare land decreased by 11.74% during the study period. The most intensive conversion of green and bare land into built-up land cover occurred in the first decade (1991–2000). To assess spatiotemporal changes in the LST, Landsat Collection 2 Surface Temperature products were used. We found a negative correlation between change in the spectral vegetation indices and change in the LST. This indicates that the reduction in vegetation was associated with an increase in the LST. The municipalities that were the most affected in each decade were also identified with our framework. The findings of this study are of great relevance for actions targeting an improvement in urban thermal comfort and climate resilience.