Thin films of polystyrene (PS) and poly(methyl methacrylate) (PMMA) were spun-cast onto silicon substrates, annealed, and analyzed by atomic force microscopy (AFM), total electron yield (TEY), and partial electron yield (PEY) near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in order to resolve conflicting prior literature regarding the tendency of PS to form a wetting layer or overlayer on top of PMMA. From the comparison of the three methods of analysis and on the basis of the extraordinary surface sensitivity of PEY NEXAFS, we conclude that PS does not form an overlayer in samples with morphologies near thermodynamic equilibrium. The PS forms droplets of a large size range on top of a PMMA layer that wets the hydrophilic SiOx substrate. From our results, the maximum thickness of a continuous PS wetting layer would be about 0.25 rim. This is in contrast to recent experiments that imply an equivalent PS wetting layer of about 5-10 nm is forming during annealing.