Two differently-structured layer-built cells have been fabricated using screen-printed LiMn2O4 and metallic Li as the electrodes, and PEO-based polymer electrolytes. Two-cathode layer-built cells (cathode/electrolyte/anode/electrolyte/cathode) and two-anode layer-built cells (anode/electrolyte/cathode/electrolyte/anode) were prepared for this study. To evaluate the layer-built cells, electrochemical cycling and ac impedance test have been performed. Of the cells tested, the layer-built cells showed improvements in polarization losses.