The selective oxidation of n-butane to maleic anhydride over V-P-O mixed oxides was studied under oxygen deficient conditions. The mixed oxides were prepared with P/V atomic ratios ranging from 0.7 to 1.0. Catalysts with P/V <1.0 did not show any selectivity to maleic anhydride formation, regardless of whether or not (VO)2P2O7 was present. For catalysts with P/V = 1.0, containing (VO)2P2O7 and/or the so-called. β-phase, the selectivity was strongly influenced by the actual surface V5+/V4+ ratio. This ratio is determined by the temperature, the crystal phases present in the catalyst and the composition of the gas mixture. Optimal selectivity was obtained at 425°C with 15% butane in air and a butane/oxygen ratio of 0.9.