We report that electrodeposition of polymer electrolyte in nanostructured electrodes has a strong influence on the electrochemical properties of thin-film Li-ion microbatteries. Electropolymerization of PMMA-PEG (polymethyl methacrylate-polyethylene glycol) was carried out on both the anode (self-supported titania nanotubes) and the cathode (porous LiNi0.5Mn1.5O4) by cyclic voltammetry and the resulting electrode-electrolyte interface was examined by scanning electron microscopy. The electrochemical characterizations performed by galvanostatic experiments reveal that the capacity values obtained at different C-rates are doubled when the electrodes are completely filled by the polymer electrolyte.