A　new　architectural　nanohybrid　multilayer　has　been　explored　and　built　on　various　substrates.　The　building　blocks　of　positive　and　negative　charged　polyelectrolyte-coated　nanoparticles　(NPs)　could　be　obtained　by　tuning　the　electrical　properties　of　the　amphoteric　oxide　NPs　in　acid　and　basic　environments.　The　nanohybrid　films　were,　thereafter,　formed　by　layer-by-layer　(LbL)　assembly　of　polycation-　and　polyanion-coated　NPs.　It　was　demonstrated　that　this　approach　could　incorporate　single　component　NPs　into　both　polycation　and　polyanion　layers,　and　in　turn　improve　the　NP　loading,　maintain　good　dispersion　of　NPs　within　the　film.　For　separation　applications,　a　dynamic　LbL　assembly　was　attempted　as　a　means　of　fabricating　such　nanohybrid　multilayers　on　both　2-D　and　3-D　polymeric　porous　substrates.　The　nanohybrid　multilayer　membrane　renders　both　much　higher　selectivity　and　flux　in　the　separation　of　solvent-water　mixtures.　Moreover,　such　assembly　of　nanohybrid　multilayers　allows　us　to　efficiently　simplify　the　procedures　by　reducing　3040-fold　process　cycles.　(c)　2011　American　Institute　of　Chemical　Engineers　AIChE　J,　2012