In this study, Terra/Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) imagery was analyzed together with in situ spatial data to examine the potential of high spatial resolution multispectral remote sensing to support the definition of energy exchanges in urban environment. The spatial distributions of physical parameters with relation to the urban energy budget were determined, and finally, taking into account the effects of different types of built-up areas and different land uses, the spatial distribution of all-wave surface net radiation balance for the center of the metropolitan city of Athens was estimated within about ¿44.5 Wm-2. The atmospheric downward longwave flux was estimated with the use of radiosonde measurements. The Santa Barbara DISORT atmospheric radiative transfer model was used for the simulation of the radiative transfer in the atmosphere. The results indicate that ASTER multispectral imagery enables a better understanding of energy aspects and their causes and effects, providing an important addition to conventional methods of monitoring the urban environment.