We present a theoretical study of the anisotropy and collection angle dependence of the oxygen K ELNES in V2O5. Ab initio bandstructure calculations were performed with WIEN97, a program package based on the full potential linearised augmented plane waves (FP-LAPW) method. An analysis of the site and angular momentum projected DOS allowed the identification of differently coordinated oxygens and the separation of the oxygen K-edge into contributions from terminal (vanadyl) oxygens, bridging oxygens and chain oxygens. The major contribution to the anisotropy of the O K-edge ELNES could be assigned to transitions at the vanadyl oxygen. Theoretical calculations predict that the extent of changes in the ELNES would be large enough for detection in collection angle dependent O K-edge measurements. A variation in the fine structure of the O K-edge with decreasing collection angle was confirmed by experiments.