Abstract: This paper studied covalent crosslinked assembly of multilayer organic-inorganic composite membranes for pervaporation performance. First,tubular ceramic substrates were pre-treated using dynasylan ameo silane coupling agents. Then,poly acrylic acid(PAA)/poly vinyl alcohol(PVA)/glutaraldehyde(GA) was dynamically assembled on to the inner surfaces of tubular ceramic substrates by LbL technique. Subsequently,the composite membranes were thermally cross-linked to form covalent bonds. The covalently crosslinked multilayers were stable,which could be used for pervaporation fields. The effects of layer numbers,filtration time,molecular weight of PVA and crosslinking temperature were investigated.Results show that the organic-inorganic tubular composite membrane shows excellent pervaporation performance for the separation of ethanol/water,and the membrane obtained with five trilayers has a permeate flux of 102 g/(m²·h) while the mass fraction of water in the permeate is 99.5%.