The main goal of this paper is to explore the radiative cooling and solar heating potential of several materials for the built environment, based on their spectrally-selective properties. A material for solar heating, should have high spectral emissivity/absorptivity in the solar radiation band (within the wavelength range of 0.2–2 μm), and low emissivity/absorptivity at longer wavelengths. Radiative cooling applications require high spectral emissivity/absorptivity, within the atmospheric window band (8–13 μm), and a low emissivity/absorptivity in other bands. UV-Vis spectrophotometer and FTIR spectroscopy, are used to measure, the spectral absorption/emission spectra of six different types of materials. To evaluate the radiative cooling potential of the samples, the power of cooling is calculated. Heat transfer through most materials is not just a surface phenomenon, but it also needs a volumetric analysis. Therefore, a coupled radiation and conduction heat transfer analysis is used. Results are discussed for the selection of the best materials, for different applications on building surfaces.