The lithium intercalation effects on the V2O5(001) surface have been investigated by means of the LCAO-Hartree-Fock method using various clusters. Considerable charge donated by Li to the host is transferred preferentially to the bridging oxygens rather than to the vanadyl oxygens or metals. A partial reduction of the vanadium center near the lithium is obtained. (C) 2003 Elsevier B.V. All rights reserved.