The rising attention to energy consumption problems is renewing interest in the applications of thermal remote sensing in urban areas. The research presented here aims to test a methodology to retrieve information about roof surface temperature by means of a high resolution orthomosaic of airborne thermal infrared images, based on a case study acquired over Bologna (Italy). The ultimate aim of such work is obtaining datasets useful to support, in a GIS environment, the decision makers in developing adequate strategies to reduce energy consumption and CO2 emission. In the processing proposed, the computing of radiometric quantities related to the atmosphere was performed by the Modtran 5 radiative transfer code, while an object-oriented supervised classification was applied on a WorldView-2 multispectral image, together with a high-resolution digital surface model (DSM), to distinguish among the major roofing material types and to model the effects of the emissivity. The emissivity values were derived from literature data, except for some roofing materials, which were measured during ad hoc surveys, by means of a thermal camera and a contact probe. These preliminary results demonstrate the high sensitivity of the model to the variability of the surface emissivity and of the atmospheric parameters, especially transmittance and upwelling radiance.