Nanosized TiO2 particles were prepared through facile sol-gel reaction by using microwave-assisted method. To investigate the effects of surfactants on the formation of TiO2, various additives (PVP, Triton X-100 and P123) were employed. The diameter of synthesized titania spheres could be controlled from 105 to 380 nm. The TiO2 particles prepared with P123 triblock copolymer showed large surface area and high pore volume. It was attributed to the fact that the pore site, where the surfactant template initially existed, was generated upon calcination process. The characteristics of prepared TiO2 nanoparticles were analyzed by using FE-SEM, TEM, XRD, FT-IR and N2 adsorption-desorption. As an application of prepared composites for water treatment, their photocatalytic performances for the degradation of methylene blue dye were examined by using UV-vis spectrophotometer under room light irradiation. The prepared TiO2 particles with Triton X-100 and P123 exhibited higher performance for methylene blue photo-degradation than that of P25. It was attributed to the effects of large specific surface area and high porosity.