Cluster model studies have been performed to examine the electronic structure and adsorption properties near structurally different oxygen sites at the (010) surfaces of vanadium pentoxide, V2O5, and molybdenum trioxide, MoO3. In addition, adsorption of hydrogen at the oxygen sites and desorption of OH groups has been studied in order to find site specific differences. The electronic properties and total energies of the clusters have been obtained from ab initio density functional theory (DFT) calculations. The surface oxygen sites are found to be ionic where bridging oxygens become more negative than terminal ones. Further, hydrogen adsorbs at all oxygen sites where binding is strongest at the bridge sites on the V2O5(010) surface whereas on MoO3(010) the terminal sites are preferred. The latter difference can be understood by simple geometric arguments, Surface OH groups formed by H adsorption and involving terminal oxygens are strongly bound to the surface whereas those involving bridging oxygens are mobile and become available for subsequent reactions.