Vanadium phosphates are important catalysts for the oxidation of alkanes, and commercial catalysts comprise a complex range of V4+ and V5+ phosphates. We used three complementary in situ characterization methodologies-powder x-ray diffraction and laser Raman and electron paramagnetic resonance spectroscopies-to show that the metastable phase omega-VOPO4 is very sensitive to many of the reactants and products of butane oxidation. A rapid transformation from omega-VOPO4 to delta-VOPO4 occurs on exposure to butane at the reaction temperature, and hence the metastable omega-VOPO4 may play a role in the formation of commercial catalysts.