The hollow fiber asymmetric matrix membranes were prepared with phase inversion by utilization of the chloromethyl polysulfone/polyethylene glycol/DMAC casting solution and chloromethyl polysulfone as membrane materials. The effects of composition of spinning casting solution and process parameters of dry-wet spinning on the structure of hollow fiber matrix membrane were investigated. Through the reaction between matrix membrane and thiourea, the highly qualified polysulfonebenzylthiourea reactive hollow fiber ultrafiltration membranes were able to afford. The adsorption isotherms of the polysulfonebenzylthiourea hollow fiber membrane for Cd2+ and Zn2+ were determined and the effects of mobile phase conditions and the operating parameters on removal performance of the polysulfonebenzylthiourea hollow fiber membrane for Cd2+ and Zn2+ were also investigated. The experimental results showed that adsorption isotherms of Cd2+ and Zn2+ could be described by the Langmuir isotherm, the polysulfonebenzylthiourea hollow fiber membrane could be operated at high feed flow rate, and a large-scale removal of Cd2+ and Zn2+ could be realized. According to required recovery of Cd2+ and Zn2+ and the saturation degree of polysulfonebenzylthiourea hollow fiber membrane, the optimum loading amount of Cd2+ and Zn2+ should be selected in the actual removal of Cd2+ and Zn2+. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114:1942-1953,2009