Promising La3+-doped electrolytes based on a hybrid poly(oxyethylene)/siliceous host matrix, U(600), have been produced. The organic and inorganic components of the hybrid structure are covalently bonded through urea linkages. The low molecular weight of the polyether segments of U(600) is thought to be responsible for the total amorphous character and high conductivity at room temperature (1.1×10−4 S cm−1) of these ormolytes.