Abstract: A novel method for the production of nanoscale polymeric multilayer films of ferroelectric PVDF/PDDA is presented. The ultrathin multilayer film of poly (diallyldimethylammonium chloride) (PDDA) and polyvinylidene fluoride (PVDF) has been prepared by the layer-by-layer static self-assembly (LbL-SA) method. The PVDF/PDDA multilayer film with the thickness ranging from about 30nm to 150 nm (the thickness of each layer is about 9nm.) is characterized by quartz crystal microbalance (QCM), atomic force microscope (AFM), X-ray diffraction (XRD), and infrared spectra (IR). The QCM reveals that the alternate ultrathin films of PVDF and PDDA are well orderly assembled. AFM results indicate that PVDF/PDDA polymeric multilayer film with high uniformity has been obtained. Compared with PVDF thick film, resistivity of PVDF/PDDA ultrathin film is dramatically enhanced.