Land use intensification and expansion in urban areas increases land surface temperature (LST). Several studies have developed to evaluate the LST and its drivers in the world, but few of them have addressed the annual and seasonal effects in urban areas located in tropical regions. This study assesses the spatiotemporal relationship between LST, green vegetation cover, and built-up areas in Brasília, Federal District, Brazil. We used time series of Landsat images (2000–2019) to retrieve the LST and compare it with the normalized difference vegetation index (NDVI), normalized difference built-up index (NDBI), and surface urban heat island (SUHI). Based on our results, the NDVI values increased from 0.46 to 0.58 between 2000 and 2019. A similar increasing trend was observed for LST (24.9 °C in 2000; 32.4 °C in 2019), which indicates that the magnitude of increase of urban vegetation cover was not able to reduce LST. The highest average LST and SUHI values were observed during local spring season (September to December; 41.9 °C and −3.2 °C, respectively). During the autumn (March to June) and winter (June to September) seasons, we observed a progressive increasing trend of the LST values. The NDVI explained 80% of the surface temperature variation within areas of native vegetation and 53% in urban areas. Based on our assessment of the spatiotemporal changes of the LST as a function of normalized difference vegetation and urban spectral indices, we provided crucial information to support urban green cover planning and management that, ultimately, will improve the population's well-being.