Vanadyl pyrophosphates ((VO)(2)P2O7) having different microstructures were prepared by calcination of vanadyl alkylphosphates (V = V4+ and P = P5+), which were synthesized with methanol, 1-butanol, and benzyl alcohol. XRD, SEM, and IR measurements revealed that these alkylphosphates were lamellar compounds and exhibited different morphologies retaining the lattice V-O-P bondings. It was found that among these precursors, vanadyl methylphosphate was superior to the others as the precursor for (VO)(2)P2O7 with the high surface area, catalytic activity, and selectivity to maleic anhydride. The catalyst obtained from methylphosphate possessed 42 m(2) g(-1) of the surface area after the reaction and exhibited 67% of the selectivity at the conversion of 52% in the oxidation of n-butane at 703 K. This high catalytic performance would be brought about by the formation of single phase of (VO)(2)P2O7 consisting of smaller crystallites.