The high surface sensitivity of Reflection Electron Energy Loss Spectroscopy (REELS) should be helpful in the characterization of systems consisting of a few monolayers on a substrate. To unravel the dependence both on the material and layer thickness a simple model of the signal formation in REELS is used which requires probabilities of different elastic and inelastic electron interactions with single atomic layers. Their estimation from experimental and theoretical results is described and discussed. The relative signal intensities are given for different systems as a function of the number of monolayers. These curves show a maximum with overlayer thickness if the probability of elastic backscattering of the substrate is higher than that of the overlayer.