A novel photocatalysis material, F-Si-comodified TiO(2) (FST) powder, was synthesized by ultrasound-assisted hydrolysis. The prepared material was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible absorption spectroscopy, respectively. XRD analysis indicated that the phase of FST was pure anatase and Si atoms suppressed the growth of titania crystalline, XPS spectra showed that FST was composed of Ti, O, Si and F element, the band gap energy of FST calculated according to the spectrum of UV-vis absorption was 3.26 eV. The electron spin resonance (ESR) spin-trapping technique using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the spin-trap reagent has been applied to detect free radical intermediates generated from FST. ESR results showed the concentration of the active species (OH) on FST is higher than those on F-doping TiO(2) (FT), Si-modifying TiO(2) (ST) and P25 titania. The degradation of pentachlorophenol (PCP) in the microwave-assisted photocatalysis (MAPC) process was faster than other processes including microwave-assisted direct photolysis (MADP), microwave process alone (MP) and dark process (DP). The photocatalytic activity of FST is much higher than that of ST, FT and P25 titania. It may be attributed to its strong capacity of absorption to the UV-vis irradiation and more hydroxyl radical on surface of FST. In MPAC process, 40 mg L(-1) PCP was completely degraded in 20 min and its corresponding mineralization efficiency was 71%, the pH of solutions decreased from 10.3 to 6.47 and the dechlorination was completed in 12 min. The intermediates products of PCP in MAPC process identified by GC/MS were trichlorophenols (TCP), tetrachlorophenols (TTCP) and tetrachlorocatechol (TTCC) and the possible mechanism of PCP degradation is proposed.