Single crystals of V2O5 and Li-0.03 V2O5 were imaged in ambient conditions by atomic force microscopy (AFM). Atomic-scale resolution images are compared with total electron-density plots of the surface calculated using the ab initio HartreeFock method. The calculated oxygen charge at the V2O5(010) surface suggests an increased local reactivity of the bridging oxygens with respect to electrophilic attacks by adsorbate molecules. The intercalation of lithium has no consequence on the reactivity of the surface. This is supported by results from electrostatic potentials calculated from the cluster charge distributions. (c) 2006 Published by Elsevier B.V.