The valence-band and core-level x-ray photoelectron spectroscopy (XPS) of vanadium phosphates are reported, and the valence-band spectra interpreted by various calculation models. The spectral interpretation of the vanadium phosphates is used to show that an oxide-free vanadium phosphate film corresponding to VO(H2PO4)(2) can be prepared on vanadium metal. Three types of vanadium phosphate were investigated to provide an understanding of the XPS data for vanadium phosphates, and to demonstrate the differences between these phosphates and vanadium oxides. The three phosphates formed, VO(H2PO4)(2), VOHPO4.0.5H(2)O, and VOPO4.2H(2)O were prepared by reaction of vanadium with phosphoric acid under a variety of conditions. The article focuses upon the valence-band region which shows significant differences between different types of vanadium phosphates as well as clear differences between the phosphates on the one hand and oxides on the other hand. The valence-band spectra are effectively interpreted by the multiple scattered-wave Xalpha calculations and band structure calculations. (C) 2003 American Vacuum Society.