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　gm(-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.　(c)　2013　Wiley　Periodicals,　Inc.　J.　Appl.　Polym.　Sci.,　2014,　131,　40004.