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.