Abstract Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS) were employed to analyze the surfaces of PVC films with poor printability. FTIR indicated that, independent of formulation, the migrating species were metal carboxylates. Different techniques penetrate the surface to different depths allowing examination of a range of surface layers. XPS indicated that, in the worst case, the upper surface layer was comprised almost exclusively of a mixed metal carboxylate. Atom percentages obtained by XPS indicated hydrolysis of the mixed metal carboxylate at the vinyl surface.