A new route towards phenol production by one-step selective hydroxylation of benzene with hydrogen peroxide over ultrafine titanium silicalites-1 (TS-1) in a submerged ceramic membrane reactor was developed, which can maintain the in situ removal of ultrafine catalyst particles from the reaction slurry and keep the process continuous. The effects of key operating parameters on the benzene conversion and phenol selectivity, as well as the membrane filtration resistance were examined by single factor experiments. A continuous reaction process was carried out under the obtained optimum operation conditions. Results showed that the system can be continuously and stably operated over 20 h, and the benzene conversion and phenol selectivity kept at about 4% and 91%, respectively. The ceramic membrane exhibits excellent thermal and chemical stability in the continuous reaction process. (C) 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.