The paper considers the application of the traditional X-ray photoelectron spectroscopy (XPS) methodology: the Overlayer Thickness Determination for the analysis of coating parameters. In particular situations considered in this work, it is energetically favorable for the atoms of the coating to form clusters, but not be evenly distributed on the surface of the substrate material. The change in the XPS signal is analyzed in situations when the coating is not a plane-parallel homogeneous layer, but an island (cluster) structure. The mathematical model of the XPS signal formation is considered for the case of the cluster covering in the form of parallelepipeds. Photoelectron path distributions (in the coating material) analysis indicated a strong dependence of the signal on the viewing angle. For the purpose of analysis, experimental spectra were obtained for several samples: gold depositions of various thicknesses on a silicon substrate. The spectra were measured for different viewing angles of photoelectrons and interpreted within the Straight Line Approximation (SLA). It is shown that proposed simplest model of an island coating allows to describe the effect of a decrease in the value of the effective average coating thickness, determined in plane-parallel geometry, with an increase in the viewing angle, observed in XPS experiments with angular resolution.