This paper analyses the thermal behaviour of the materials, which are widely used on the vertical surfaces of Greek cities. This analysis is based on surface temperatures measurements, which were carried out both in situ in various buildings of Athens, Greece and experimentally on samples of building materials exposed to solar radiation on a building's flat roof. The study includes surfacing materials, which are usually applied on building facades around Greece. The study leads to a number of conclusions concerning the effect of colour and orientation on the summer surface temperatures of materials, used on vertical city surfaces. These conclusions indicate how surfacing materials should be chosen in order to help mitigate the urban heat island and improve thermal comfort conditions in the outdoor spaces of Greek cities during the overheated summer period. (C) 2008 Elsevier Ltd. All rights reserved.