Surface-modified inorganic powders were applied as additives to plain salt-in-polymer polymeric electrolytes in order to enhance their properties and make them applicable in all-solid-state Li-polymer primary and secondary cells. These fillers consisted of alumina and titania powders (coarse and nano-sized) with superacidic groups introduced onto their surface. Then they were added to low and high molecular weight poly(ethylene oxide) (PEODME 500 and PEO 4,000,000) together with lithium perchlorate (LiClO 4, lithium tetraoxochlorate(VII)). In this way several different composite electrolytes were obtained that exhibited excellent stability versus lithium metal electrode and high lithium transference number. Herein the preparation procedure is described and preliminary results given.