Phosphorus L-edge and oxygen K-edge X-ray PhotoEmission Electron Microscopy (XPEEM) have been used to characterize the chemical nature of the cation present in tribochemical films via comparison with model Fe2+ and Zn2+ compounds. The results are contrasted to the P L-edge, P K-edge and S K-edge XANES data. The findings suggest that antiwear pads containing long chain zinc polyphosphate glass are formed at the points of asperity contact, and a thin, short chain zinc polyphosphate film is formed where no asperity contact is made. SEM/EDX measurements helped to elucidate the distribution of the elements, and strong spatial correlations were observed between P, O, Zn and S in the pads, indicating that they are composed mostly of zinc polyphosphates, especially near the surface. The zinc polyphosphate antiwear pads are characterized by a much lower modulus than that observed on the thin film regions, the latter being characteristic of the substrate steel.