Abstract: B-ZSM-5 zeolite with a smaller crystal size and a suitable amount of framework boron was synthesized by modifying hydrothermal synthesis temperature.Ti-ZSM-5 zeolite was prepared by the gas-solid reaction of acid-treated B-ZSM-5 with gaseous TiCl₄.The samples were characterized by SEM,XRD,FT-IR,UV-Raman and UV-Vis.The performance of Ti-ZSM-5 in phenol hydroxylation was investigated.The results showed that the smaller sized Ti-ZSM-5 samples had MFI topology structure and high crystallinity, higher content of framework titanium and no extra-framework titanium.The optimal reaction conditions of phenol hydroxylation over Ti-ZSM-5 were as follows: acetone as solvent, reaction temperature 343—363 K, the mass ratio of catalyst to phenol 5.0%—10.0%, the molar ratio of phenol to hydrogen peroxide 3—6,reaction time 3—6 h.Phenol conversion could be more than 23%.