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