Supramolecular templating and layer-by-layer deposition were combined to synthesize multilayered mesoporous TiO2 films of high mesopore order and micrometer scale thickness for application in dye-sensitized solar cells. The photovoltaic performance of the supramolecular-templated mesoporous TiO2 film is dependent on the film thickness and the pre-curing temperature by tuning the crystallinity, surface area, and interfacial adhesiveness of the film to substrate. A maximum efficiency of 5.12% was achieved for the mesoporous TiO2 film at the thickness of 2.20 mu m and pre-curing at 250 degrees C. (C) 2010 Elsevier B.V. All rights reserved.