The surface and bulk compositions of vanadium molybdenum oxynitride (V2MoO1.7N2.4), prepared by temperature-programmed reaction (TPR) of vanadium molybdenum oxide (V2MoO8) with ammonia, have been characterized using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS data were recorded at the K-edges of nitrogen and oxygen, the L-edge of vanadium, and the M-edge of molybdenum. The nitrogen K-edge region of V-Mo oxynitride shows the characteristic NEXAFS features of early-transition-metal nitrides, although these features are different from those of either VN or Mo2N. Furthermore, comparison of the electron yield and fluorescence yield measurements also reveals that the oxidation state is different for vanadium near the surface region and for vanadium in the bulk, which is estimated to be 2.8 +/- 0.3 and 3.8 +/- 0.3, respectively. The oxidation state of bulk molybdenum is also estimated to be 4.4 +/- 0.3. The X-ray diffraction pattern shows that the bulk phase of the bimetallic oxide is different from the pure monometallic oxide phases but the oxynitride has a cubic structure that resembles the pure vanadium and molybdenum nitride phases. The V-Mo oxide as prepared shows a preferential orientation of [001] crystallographic planes which is lost during the nitridation process. This shows that the solid state transformation V2MoO8 --> V2MoO1.7N2.4 is not topotactic. The hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) activities of V-Mo oxynitride are also compared to those of either VN or Mo2N catalysts. The bimetallic V-Mo oxynitride catalyst shows higher HDS, HDN, and HDO activities than those of the monometallic nitride catalysts.