Several kinds of chloromethyl polysulfones (CMPSF) with different chlorinity and reactive groups were synthesized by Friedel-Crafts reaction, which could be utilized as reactively matrix membrane materials. The CMPSF hollow matrix membranes were prepared with phase inversion by utilization of the CMPSF/additive/DMAC casting solution and CMPSF as membrane materials. The rheological behavior of CMPSF/additives/DMAC spinning casting solution was studied. The experimental results showed that the spinning casting solution was a pseudoplastic fluid, the apparent viscosity of the spinning casting solution decreased with the increase of shearing rate, and the viscous flow activity energy of the spinning casting solution was inclined to unchange at high shearing rate. The effects of composition of spinning casting solution and process parameters of dry-wet spinning on the structure of CMPSF hollow fiber matrix membrane were investigated. The pore size, porosity, and water flux of membrane decreased with the increase of additive content, bore liquid, and dry spinning distance. With the increase of extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow fiber matrix membrane increased, but the pore size and water flux of the membrane decreased. It was also found that the effects of internal coagulant composition and external coagulant composition on the structure of CMPSF hollow fiber matrix membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of CMPSF hollow fiber matrix membrane and decrease the pore size, porosity, and water flux of the CMPSF hollow fiber matrix membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the CMPSF hollow fiber matrix membrane. (c) 2006 Wiley Periodicals, Inc.