The interactions of VOHPO4 . 0.5H(2)O and (VO)(2)P2O7 with the ammoxidation feed and the single components such as ammonia, oxygen, water and component mixtures were studied in detail using XRD and temperature-programmed reaction spectroscopy. The aim of this work Ras to improve the knowledge of the formation oi the active phases or active sites of the catalysts from their precursors under the condition of the ammoxidation reaction. Similar catalytic properties of various applied VPO materials were discussed in terms of the presence of similar structure elements (domains of adjacent edge-sharing VO6 octahedra-units and P-O-NH4 groups).