Lithium trifluoromethanesulfonate:polyethylene oxide (PEO) polymer electrolytes modified by 1,1,3,3,5,5-meso-hexaphenyl-2,2,4,4,6,6-meso-hexamethyl-6-pyrrole (C6P) and nanosize silica filler were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and electrochemical means. An increase in the lithium transference number is observed upon incorporation of even a small amount of C6P. Silica facilitates interchain ion hopping in polymer electrolytes and possibly introduces an additional interfacial ion-conduction path without decreasing t +. Stable solid electrolyte interphase resistance (SEI) was achieved in the polymer electrolytes containing calix[6]pyrrole and silica. It was found that lithium single-ion-conductive polymers with good electrochemical stability and ion transport properties have the potential for considerably boosting the performance of lithium/molybdenum oxysulfide all-solid-state thin film batteries.