The integration of microclimatic information and energy balance of the materials into urban design is essential for adequately addressing the challenges related to climate change and to adaptation of urban environment to new climatic loads. Several studies model the urban climate from multispectral satellite measurements. However, the remotely sensed measurements usually have a spatial resolution of several meters and are not suitable for determining microclimate effects in urban areas and on individual buildings. Moreover, they require consideration of the intervening atmosphere and the surface radiative properties that influence the emission and reflection of radiation within. The present research approach includes in-situ measurements and aerial surveys with VIS/NIR multispectral camera and IR camera mounted on a UAV. Analysis presented here, aims (1) to identify physical characterization of reflectance properties in a variety of urban settings in Athens, (2) to explore the response of vegetation, cool and conventional materials in the NIR region (3) to study climate parameters essential to the bio-climatic design in this urban cover (4) to elaborate observational studies for obtaining better validation of the surface effective parameters derived. The sensors on UAVs provide a unique perspective of urban features for revealing the complex mechanisms that lead to micro-climatic modifications and to quantify their relative contribution. The application of NIR images in building and urban scale analysis is innovative and reveals different properties of the surface of the objects.