Water adsorption on the surface of LiCoO2 nanoparticles was investigated. As the water coverage increases the adsorption enthalpy decreases reaching the enthalpy of water condensation (-44kJ mol-1). The experimentally observed average surface energy corresponding to all facets agree well with those reported from DFT calculations. The observed low surface energy is attributed to the surface Co3+ spin transition in nanophase LiCoO2. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.