Neutron and X-ray scattering studies of (Li2O2)(x)-(TeO2)(2)-V2O5 glasses with x = 0, 1 and 2, obtained by melting and subsequent cooling in air to room temperature, have been performed. Reciprocal space data have been Fourier transformed into real space yielding the radial distribution functions. Nearest and next neighbor peaks have been analyzed using a least-squares fitting method which suggests the presence of both TeO3 and TeO4 coordination polyhedra, the fivefold coordination of lithium and mixture of 6, 5 and 4 coordination numbers of vanadium. These results are discussed in relation to the electronic and ionic conductivity properties. (c) 2005 Published by Elsevier B.V.