This study aims to evaluate the thermal field of the central business district (CBD) of Rio de Janeiro during summer from land surface temperature (LST) and the thermal characteristics of the urban canopy layer (UCL) of the urban canyon in Avenida Rio Branco. In order to conduct this evaluation, two methods were employed: (1) TIRS Landsat-8 sensor for data selection and processing (latest generation, 2011–2020); (2) a field survey using nine sampling points—seven along two mobile transects, one fixed point, and one vertical measurement point, which required the use of an RPA (remotely piloted aircraft). Three categories of analysis were established for the field survey based on the prevailing synoptic situations: stability, instability, and post-instability. The CBD is characterized by extensive areas with surface heat islands, in which temperatures were higher than 38.9 °C; the areas with milder LSTs were Campo do Santana, Avenida Rio Branco, and one of the mixed-use zones (Praça Mauá). With respect to Rio Branco Avenue, the LST niches of lowest elevation were derived through building shadowing; however, due to the nature of the data, the orbital data diverged from the observation data of the 10 field-study days. In situ data revealed that the characteristics urban morphology of Avenida Rio Branco, by contrast with the LST result, is susceptible to the formation of atmospheric heat islands, presenting heat islands of very strong magnitude (over 6.1 °C) in atmospheric stability, strong magnitude (4.1–6.0 °C) in atmospheric instability, and moderate magnitude (2.1–4.0 °C) in post-atmospheric instability. Despite the synoptic situation, thermal cores were concentrated at 1 p.m. The intersection between Avenida Rio Branco, Rua do Ouvidor, and Praça Mauá stored most of the solar energy received during the day due to the greater sky obstruction caused by the verticalization. Finally, vertical analysis demonstrated the formation of a thermal inversion on the night of the highest mean air temperature (29.5 °C), probably due to the roughness and number of buildings in the urban canyon.