Lithiation characteristics of a complex oxide containing V(V) and Cu(II), alpha-CuV2O6, were investigated. Lithiation was carried out chemically using an n-BuLi/hexane solution. The valence states of copper and vanadium and the structural changes upon lithiation were analyzed using ESR, XRD and OCV measurements. It was revealed that reduction processes occurred consecutively with an increasing extent of lithiation, x = Li/(Cu + 2V) and Cu(II) component was reduced to Cull) preferentially over V(V). The Single phases exist at 0 < x < 0.35 and 1.5 < x < 2.0, and at 0.35 < x < 1.5 and 2.0 < x < 3.0 lithiation occurs in multi;phases of the original and the second phases and the second and Cu(O) phases, respectively. Electrochemical lithiation behaviours of a series of the complex oxides nCuO . V2O5 were compared by the galvanostatic intermittent titration technique.