In this study, an in situ crosslinked polydimethylsiloxane/brominated polyphenylene oxide (c-PDMS/BPPO) membrane on ceramic tube has been prepared for the recovery of butanol by pervaporation. A series of BPPO with different bromide-substituted ratio were firstly synthesized through Wohl–Ziegler reaction. BPPO and PDMS were sequentially assembled and in situ crosslinked to form the final c-PDMS/BPPO membrane. The results of solid-state NMR and Differential Scanning Calorimeter demonstrated that the c-PDMS/BPPO copolymer has a crosslinking structure and the SEM result proved the coverage of ceramic tube by copolymer layer. The effects of preparation conditions including dipping time and bromide-substituted ratio of BPPO on the membrane performance were studied. The pervaporation experiments of butanol–water mixture indicated that the c-PDMS/BPPO membrane exhibited an acceptable flux of 220 g·m−2·h−1 and high separation factor of 35 towards butanol, when the bromide-substituted ratio was 34 wt % and the dipping time was 1.33 h. Moreover, the c-PDMS/BPPO membrane performed excellent stability in an about 200 h continuous butanol recovery, as compared to the PDMS membrane. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40004.