This paper proposes a new approach of using a spin-coated solid polymer electrolyte in the fabrication of an all-solid-state rechargeable thin-film lithium battery with the cell structure of Li/polymer/LiMn2O4. Room temperature cycling of this cell showed comparable cycling performance and good Coulombic efficiency at the 6C rate (100μAcm−2). On removing the spin-coated solid polymer electrolyte after the cycle test, we observed a morphology change on the LiMn2O4 cathode surface using a field emission scanning electron microscope (FE-SEM). FE-SEM also showed that there had been dissolution/precipitation of manganese species at the cathode/electrolyte interface during cycles.