This paper describes the synthesis and properties of a new type of ceramic fillers for composite polymer gel electrolytes. Hybrid TiO2-SiO2 ceramic powders have been obtained by co-precipitation from titanium(IV) sulfate solution using sodium silicate as the precipitating agent. The resulting submicron-size powders have been applied as fillers for composite polymer gel electrolytes for Li-ion batteries based on polyacrylonitrile (PAN) membranes. The powders and gel electrolytes have been examined structurally and electrochemically, showing favorable properties in terms of electrolyte uptake and electrochemical characteristics in Li-ion cells.