The　ferroelectric　ultrathin　multilayer　of　PDDA/PVDF-BT　were　fabricated　on　the　pretreated　quartz　substrates　between　cationic　electrolyte　of　poly(diallyldimethyl　ammonium　chloride)　(PDDA)　and　anion　reagent　by　electrostatic　self-assembly　method.　Negatively　charged　poly(vinylidene　fluoride)　(PVDF)　dispersed　with　inorganic　BaTiO3　nano-granules　in　organic　solvent　was　using　as　anion　reagent.　The　thickness　of　the　12-layer　ferroelectric　composite　ultrathin　films　characterized　by　quartz　crystal　microbalance　(QCM)　is　about　82　nm,　and　there　exists　a　nearly　linear　relationship　between　the　thickness　and　layer　number　of　ultrathin　films.　The　results　of　SEM　and　XRD　show　that　the　composite　ultrathin　films　are　deposited　on　the　quartz　surface　smoothly　and　densely　with　uniform　distribution　of　BaTiO3　nano-granules,　and　excellent　crystalline　performance.　The　hysteresis　loop　of　ferroelectric　composite　ultrathin　films　shows　that　the　electric　polarization　of　the　composite　ultrathin　films　is　increased　to　3　μC/cm2.