Band-structure (BS) calculations of the density of states (DOS) using the full potential augmented plane waves code WIEN97 were performed on the four single-valence vanadium oxides VO, V2O3, VO2 and V2O5. The DOS are discussed with respect to the distortions of the VO6 octahedra, the oxidation states of vanadium and the orbital hybridisations of oxygen atoms. The simulated oxygen K-edge fine structures (ELNES) calculated with the TELNES program were compared with experimental results obtained by electron energy-loss spectrometry (EELS), showing good agreement. We show that changes in the fine structures of the investigated vanadium oxides mainly result from changes in the O-p DOS and not from the shift of the DOS according to a rigid band model.