This study concerns quantum chemical modeling of water behaviour on V-W-O systems. It was undertaken in order to validate the hypothesis that the presence of W atoms on (001) surface of the crystalline vanadia-like species, facilitates low temperature water dissociation. Quantum chemical calculations were done with the use of modern electronic structure methodology, based on the density functional theory (DFT). The program package DMol of Molecular Simulations, was applied for the calculations. The calculations were performed for small clusters representing two adjacent metal sites, in pentacoordinated oxygen environment, analogous to bipiramidal clusters, introduced in description of the (001) layers of vanadium pentoxide.