There is an increasing trend in the utilization of highly nanostructured materials, especially as light absorbers or chemical gas sensors. However, for most applications a more detailed study of surface processes and phenomena is necessary or at least highly beneficial.The present paper describes the surface processes of black aluminum prepared by different PVD methods (magnetron sputtering at room and liquid nitrogen temperature, and thermal evaporation) studied by thermally stimulated exoelectron emission. The actual investigation of the interaction between surface and adsorbed atoms and molecules was carried out after UV irradiation. For the samples prepared in this way, thermostimulated exoelectron emission was measured in the temperature range: liquid nitrogen temperature to 400 °C. SEM analysis revealed significant differences in the morphology of the layers, which were associated with a change in the position of the maxima in the thermostimulated exoelectron emission spectra.The activation energies for the electron emission were calculated. The binding process on the surface of the individual samples and their dependence on the type of black aluminum thin film preparation were described.The results could determine which type of thin film preparation is suitable for use as chemical gas sensors.