This work is a continuous of our previous work in M.Sc study. Our previous work was concerned with the use of locally produced V2O5 (technical grade) in the preparation of catalyst successfully employed in the oxidation of n-butane to Malice Anhydride. The catalyst was evaluated using geomechanic system (France) specially built for catalytic test and modified to our proposes. The results had indicated to a functional catalyst. The catalytic properties were attributed to several factors (highly disordered, P/V around 1.1, adequate specific surface area, preparation method and other factors) (1). Since the catalytic activity of Vanadyl Acid Phosphate towards the reaction of n-butane oxidation to maleic anhydride (MA) was achieved in our previous work. It is useful to study the effect of addition (TiO2) anatase as a support on structural properties and surface chemistry of the catalyst. This precursor is prepared in an alternative method never mentioned in the literature. Route (A) depends on the reaction of the technical grade (V2O5) with (o- H3PO4 ) in order to prepare the intermediate phase (VOPO4.2H2O) which is then reduced by a mixture of (benzyl alcohol and isobutanol) to reach the assigned phase VO (H2PO4)2 . While the traditional route (B) depends on the reduction of vanadium pentoxide by alcohol mixture and then adding phosphoric acid to the reduced phase. The structural properties and surface chemistry of vanadyl acid phosphate and the intermediate phase prepared by route (A) and vanadyl hydrogen phosphate hemihydrate prepared by route (B) are studied after carrying out physical and chemical analysis in international known laboratories in U.S.A, Germany, Republic of Ukraine and U.A.E. by using special techniques devoted in catalytic structural and surfaces studies. The identification of the prepared phases was carried out by using X- ray diffraction (XRD). The results of phases identification show the co- existence of traces of other phases like VO (H2PO3)2 with the dominated main phase prepared by rout (A). These results also indicate that a very pure phase was never reached phase which is known phenomenon in the field of preparation of (VPO) system. It was found through these identification examination that the addition of TiO2 (anatase) could affect the resultant phases prepared in rout (B), since a monohydrate composition (VOHPO4.H2O) is obtained instead of Vanadyl Hydrogen Phosphate Hemihydrate (VOHPO4.0.5H2O) normally prepared without the use of support . No effect of support is observed on the main phase prepared by route (A). The differential thermogravimetric behaviors for the precursors were studied.