We investigated the electronic structure of epitaxially grown silver films on Cu(111) with and without adsorption of cesium by means of scanning tunneling spectroscopy and two-photon photoemission. This system has been chosen as a model system to engineer and measure the dynamics of charge-transfer processes between an adsorbate and a heterogeneous substrate. Special emphasis has been laid on the investigation of the energy shift of the Shockley-type surface state and an excited cesium resonance as a function of Ag film thickness. For the cesium resonance we observe an increase in line width with increasing layer thickness.