Multilayer　membranes　constructed　layer-by-layer　(LbL)　is　finding　increasing　importance　in　many　separation　applications.　The　efficient　construction　of　LbL　multilayer　on　to　hollow　fiber　substrates　may　offer　many　new　opportunities　for　industrial　applications.　An　organicinorganic　composite　hollow　fiber　membrane　has　been　developed　using　a　dynamic　LbL　self-assembly.　This　poly(acrylic　acid)/poly(ethyleneimine)　multilayer　was　dynamically　assembled　onto　the　inner　surfaces　of　ceramic　hollow　fiber　porous　substrates　pretreated　by　Dynasylan　Ameo　silane　coupling　agents.　The　hollow　fibers　were　subsequently　heat　crosslinked　to　obtain　stable　permselective　membranes.　The　formation　of　multilayers　on　the　hollow　fibers　was　characterized　with　a　SEM,　EDX,　an　electrokinetic　analyzer　and　IR　spectra.　The　effects　of　layer　number,　feed　temperature　and　water　content　in　the　feed　on　the　pervaporation　performance　have　been　investigated.　To　the　best　of　our　knowledge,　this　is　the　first　report　of　LbL　assembly　of　polymer　building　blocks　onto　ceramic　hollow　fiber　porous　substrates.　(c)　2011　American　Institute　of　Chemical　Engineers　AIChE　J,　58:　31763182,　2012