Various experimental results on hydrogen spillover which have been obtained since the first evidence for this phenomenon are discussed concerning the nature of the activated hydrogen species. It will be demonstrated that the physical nature of the spilt-over species, especially their charge, can only be described by considering their interaction with the solid. A new model is proposed which is based on the description of spilt-over hydrogen as electron donor located at the surface. Consequently, H⁺ ions and H atoms coexist on the surface of the catalyst as also stated experimentally. Their ratio is determined by the electronic properties of the adsorbate/solid system. Considering atomic and recombinative desorption of spilt-over hydrogen, the adsorption isotherms are calculated exemplary for titania. The model is applied to interpret some experimental results related to hydrogen spillover, especially the partial electron transfer from the hydrogen species to the solid.