For smooth surfaces, chemical composition can be readily analyzed using various spectroscopic techniques, a prominent example is X-ray photoelectron spectroscopy (XPS), where the relative proportions of the elements are mainly determined by the intensity ratio of the element-specific photoelectrons. However, this analysis becomes more complex for nanorough surfaces like black silicon (b-Si) due to the geometry's steep slopes, which mimic local variations in emission angles. In this study, this effect is explicitly quantified through an integral geometric analysis using Minkowski tensors, correlating XPS chemical data with topographical information from Atomic Force Microscopy (AFM). This approach yields reliable estimates of layer thicknesses for nanorough surfaces. For b-Si, it is found that the oxide layer is ≈50%–80% thicker than the native oxide layer on a standard Si wafer. This study underscores the significant impact of nanoscale geometries on chemical property analysis.