The cycling performance of all-solid-state, scaled-up, 0.6Ah Li/V2O5 polymer battery prototypes, realized within a National Project devoted to development of electric vehicles, is presented and discussed. Poly(ethyleneoxide)–LiN(SO2CF2CF3)2 (PEO–LiBETI) films were used as electrolyte separators. The prototypes, formed by parallel stacking ten single bipolar cells, were assembled by the direct lamination of the components, namely, lithium foil anodes, PEO–LiBETI electrolyte films and composite V2O5-based cathode films. The performance of the Li/PEO–LiBETI/V2O5 prototypes, scaled-up from single cells, was evaluated in terms of specific capacity, energy and cycle life at different discharge current densities. The results have indicated high reproducibility of the manufacturing process and the feasibility to large scale-up the all-solid-state, lithium polymer batteries based on solvent-free prepared PEO–LiBETI electrolyte.