The layer-by-layer self-assembly of poly(diallyldimethyl-ammonium) chloride, PDDA; graphite oxide, G, nanoplatelets; and polyethylene oxide, PEO, onto transparent indium tin oxide substrates, S, have provided cationic working electrodes which, with lithium wires as reference and counter electrodes, functioned as high energy density rechargeable lithium-ion batteries. Specifically, very high specific capacities (1232 and 1134 mAh.g−1) have been determined for batteries which had positive electrodes of ten sandwich layers of self-assembled films: S-(PDDA/GO/PEO)10and S-(PDDA/PEO)10. The importance of the exfoliating GO into nanoplatelets and the colloid chemistry of self-assembly are discussed.