Electric-field-enhanced　layer-by-layer　(LbL)　assembly　of　polyelectrolyte　and　nanohybrid　multilayers　onto　insulating　rigid　substrates　was　successfully　accomplished　using　two　independent　capacitor　cells.　The　influence　of　external　electric　field　on　the　multilayer　formation　was　intensively　investigated　by　UV-vis　adsorption　spectrometry,　profilometry,　atomic　force　microscopy,　and　small-angle　X-ray　diffraction.　This　approach　was　also　attempted　as　a　means　of　fabricating　selective　layer　on　flat　sheet　polymeric　porous　substrates　to　obtain　the　dense　composite　membranes　with　high　pervaporation　performance.