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Titanium dioxide (TiO2) films with rod-like and sphere-like TiO2 particles were prepared on glass slides employing the sol-gel method. The shape and size of TiO2 particles were controlled using different concentrations of sodium dodecylbenzensulfonate (SDBS). By increasing the mole ratio of SDBS, the shape of TiO2 particles transformed from rod-like to sphere-like. Also, the size of TiO2particles became gradually smaller. Then, the size became bigger when an excess amount of SDBS was added. The films were mainly composed of anatase titania and the relative content of anatase increased with the increasing amount of SDBS. The photocalalyfic activity of the TiO2 films that were added with SDBS was higher than that without SDBS. When the concentration of SDBS was 8.0 at%, the sample exhibited the best photocatalytic activity.