This paper reports the preparation of a core-shell nanoporous electrode consisting of an inner TiO 2 porous matrix and a thin overlayer of Al 2 O 3 , and its application for solid-state dye-sensitized solar cell using p-CuI as hole conductor. Al 2 O 3 overlayer was coated onto TiO 2 porous film by the surface sol-gel process. The role of Al 2 O 3 layer thickness on the cell performance was investigated. The solar cells fabricated from Al 2 O 3 -coated electrodes showed superior performance to the bare TiO 2 electrode. Under illumination of AM 1.5 simulated sunlight (89mW/cm 2 ), a ca. 0.19nm Al 2 O 3 overlayer increased the photo-to-electric conversion efficiency from 1.94% to 2.59%.