The thin Nb(2)O(5) layer works as a remarkable blocking layer when deposited by the rf magnetron sputtering method between fluorine-doped tin oxide and a mesoporous TiO(2) layer, improving open-circuit photovoltage (V(oc)) and fill factor (FF) with power conversion efficiency over 5.5% at 1 sun irradiation of the dye-sensitized TiO(2) solar cells using ionic liquid electrolytes.