The gas-phase catalytic oxidation of benzene over copper supported on HZSM-5 added with titanium (Cu/Ti/HZSM-5) was carried out by using molecular oxygen as an oxidant. Phenol was effectively produced by the titanium addition to Cu/HZSM-5. The titanium addition to Cu/HZSM-5 induces the easy reduction of Cu2+ species to Cu+ species in the catalysts, and the produced Cu+ species seems to produce the phenol effectively.