Electrochemical lithium insertion into alpha-type vanadium oxide bronze M(2+)-V2O5 (M=Ni, Mn, Co, Cu) of orthorhombic system was studied, by comparing with V2O5. The amount of lithium inserted into M(2+)-V2O5 bronzes up to the second plateau was smaller by about 0.15 mol than the case of V2O5 on open circuit voltage (OCV) curves and discharge curves. These results prove that M(2+) cations in the bronze are placed in the same sites as lithium between the layer of V-O polyhedra and that the number of foreign ions which can be inserted is governed by the number of sites.