The catalytic polymeric hollow fibers, PVP-Pd/CA, PVP-Pd/PSF, PVP-Pd/PAN, EC-Pd/CA and AR-Pd/CA (PVP = polyvinylpyrrolidone, EC = ethyl cellulose, AR = melamine-formaidehyde resin, CA = cellulose acetate, PSF = polysulfone, PAN = polyacrylonitrile), were prepared by supporting the soluble polymer anchored palladium complexes of PVP-Pd, EC-Pd and AR-Pd on the corresponding CA, PSF and PAN hollow fibers, respectively. These catalytic polymeric hollow fibers were used to establish the catalytic membrane reactors, and the selective hydrogenation of conjugated dienes was carried out in reactors under mild conditions of 40 degrees C and 0.1 MPa. All of the catalytic hollow fibers are active and stable for the hydrogenation of conjugated dienes. The selectivity for the formation of monoene and the conversion of diene can simultaneously be up to more than 91% in the membrane reactors established with the PVP-Pd/CA and PVP-Pd/PAN catalytic hollow fibers.