Polyvinyl alcohol [PVA]-iodine complex doped mesoporous TiO2 (PIT) and iodine doped (IT) catalysts were prepared by hydrothermal method, using tetrabutyl titanate as precursor, potassium iodate and iodine as iodine sources. The as-prepared PIT and IT catalysts were characterized by UV-vis, XRD, FESEM, BET, TG/DTA, XPS and photoluminescence (PL) spectroscopy. Production of (OH)-O-center dot radicals on the surface of photocatalyst was detected by the PL technique using terephthalic acid as a probe molecule. The influences of calcinated temperature on the structure and properties of the catalysts were investigated. The photocatalytic activity of catalysts was evaluated through photocatalytic decolorization of methylene blue (MB) aqueous solution. The results showed that PIT samples were anatase mesoporous TiO2 and their iodine content and mesoporous structure were influenced by calcinated temperature. Particle size of PIT samples was smaller than that of IT as a result of the PVA skeleton and regular structure. Because of the complexation of iodine and PVA, thermostability of iodine is improved and the amount of iodine in PIT calcinated at 200 degrees C (PIT-200) is higher than that of IT calcinated at same temperature. Light absorption range and intensity of PIT-200 has been greatly improved due to the synergy of iodine and carbon. The efficiency of photocatalysis for MB is greatly improved with TiO2 modified by PVA-I complex under simulated sun light irradiation. (c) 2013 Elsevier B.V. All rights reserved.