A VPO system was prepared from boiler-ash. VO(H2PO4)(2) phase has been obtained at low temperature and characterized through a combination of techniques including TG-DTA analysis, X-ray powder diffraction and FT-Raman spectroscopy. The thermal decomposition of the precursor material gives a VO(PO3)(2) and V(PO3)(3) phase mixture. Supported and unsupported catalysts prepared were compared and contrasted in the partial oxidation of methane (POM). The catalysts were more selective to C-1-hydrocarbons than a VPO catalyst prepared by the conventional method and studied in similar conditions. Thus, the selectivity to C-1-oxygenates was similar, however, the selectivity to COx products was hindered. The observation that the precursor VO(H2PO4)(2) Obtained from boiler ash as recovery and precipitation of the vanadium can generate catalysts of low selectivity to total oxidation products might provide a useful insight into the design of a new series of high activity and high selectivity partial oxidation catalysts.