In order to develop high performance composite membranes for alcohol permselective pervaporation (PV), poly (dimethylsiloxane)/ZIF-8 (PDMS/ZIF-8) coated polymeric hollow fiber membranes were studied in this research. First, PDMS was used for the active layer, and Torlon (R), PVDF, Ultem (R), and Matrimid (R) with different porosity were used as support layer for fabrication of hollow fiber composite membranes. The performance of the membranes varied with different hollow fiber substrates was investigated. Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers. The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated. The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect. Based on the result, ZIP-8 was introduced to prepare more selective separation layer, in order to improve the PV performance. The PDMS/ZIF-8/Torlon (R) membrane had a separation factor of 8.9 and a total flux of 847 g.m(-2).h(-1). This hollow fiber PDMS/ZIF-8/Torlon (R) composite membrane has a great potential in the industrial application. (C) 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.