Effects of the spherical shape of a small size (< 1 mum) powder and the thickness of a uniform overlayer on the surface elemental compositions measured by X-ray photoelectron spectroscopy (XPS) have been studied. The angular and radial dependence of the path length of photoelectrons generated within the substrate and the overlayer was taken into account in the calculation. The difference in photoelectron inelastic mean free path (IMFP) between the substrate and the overlayer was also considered in calculating the photoelectron intensity. Spherically shaped zinc oxide powder coated with a hydrocarbon overlayer was taken as an example.