We prepared highly oriented ferroelectric poly(vinylidene fluoride) (PVDF) Langmuir-Blodgett (LB) nanofilms by an assistance of amphiphilic poly(N-dodecylacrylamide) (pDDA) nanosheets. In the nanofilms, semi-crystalline PVDF contains abundant polar crystals, a parallel packing of PVDF all-trans molecules. Combing semi-conductive PEDOT:PSS and ferroelectric PVDF LB nanofilms, we fabricated a sandwiched capacitor (Al/PVDF LB nanofilm/PEDOT:PSS/Al). The capacitor shows asymmetric hysteresis curves and high remanent polarization values.