We report the physical and electrical characterization of a series of substituted imidazolium-based ionic liquids grafted on Stöber-type SiO2. This hybrid architecture affords an increase of the lithium transference to 0.56 by hindering TFSI- (bis(trifluoromethane)sulfonimide) mobility to the total ionic conductivity. When doped with 16 wt % wt LiTFSI, the resulting hybrid organic/inorganic solid material exhibits a lithium diffusion coefficient of 2 × 10-12 m2/s at 87 °C and a conductivity of ca. 10-6 S/cm at room temperature and 10-4 S/cm at 65 °C with an activation energy barrier of 0.89 eV.