TiO2 nanoparticles capped with sodium dodecylbenzenesulfonate (DBS) are synthesized by a sol-hydrothermal process using tetrabutyl titanate and DBS as raw materials. The effects of surface-capping DBS on the surface photovoltage spectroscopy (SPS), photoluminescence (PL) and photocatalytic performance of TiO2 nanoparticles are principally investigated together with their relationships. The results show that the surface of TiO2 nanoparticles can be well capped by DBS groups while the pH value and added DBS amount are controlled at 5.0 and 2% of TiO2 mass weight, respectively, and the linkage between DBS groups and TiO2 surfaces is mainly by means of quasi-sulphonate bond. The intensities of SPS and PL spectra of TiO2 obviously decrease after DBS-capping, while the activity can greatly increase during the photocatalytic degradation of Rhodamine B (RhB) solution, which are mainly attributed to the electron-withdrawing character of the DBS groups. Moreover, the enhancement of photocatalytic activity of DBS-capped TiO2 is also related to the increase in the capability for adsorbing RhB. (c) 2005 Elsevier B.V. All rights reserved.