A　covalent　assembly　was　accomplished　onto　hollow,fibers　via　a　dynamic　pressure-driven　layer-by-layer　(LbL)　technique.　The　covalent　crosslinking　multilayers　were　successfully　formed　onto　the　inner　surfaces　of　hollow　fiber　porous　substrates　during　the　alternatively　filtration　of　polyethyleneimine　(PEI)　and　glutaraldehyde　(GA)　solutions.　The　formation　of　covalent　bond　between　PEI　and　GA　was　confirmed　using　fourier　transform　infrared　(FTIR)　spectra.　The　thickness　increment　on　a　quartz　slide　clearly　suggested　the　stepwise　growth　of　multilayer　at　nanometer　scale.　The　regular　alternation　of　zeta　potentials　demonstrated　that　the　successful　formation　of　GA-crosslinked　PEI　multilayers　on　the　hollow　fibers.　The　multilayer　membranes　showed　excellent　pervaporation　performances　for　the　dehydration　of　different　solvent-water　mixtures.　The　selectivity　and　permeability　can　he　controlled　by　varying　the　PEI　layer　number.　More　importantly,　the　covalent　assembled　multilayer　membrane　rendered　much　higher　stabilities　compared　with　those　from　electrostatically　LbL　assembly,　which　offers　much　opportunity　for　practical　applications.　(C)　2010　American　Institute　of　Chemical　Engineers　AIChE　J,　57:　2746-2754,　2011