This paper presents crystalline structures, surface morphology, and improved ferroelectric response in ultrathin film of 70 mol % vinylidene fluoride and 30 mol % trifluoroethylene copolymer with 22 nm thickness. Remanent polarization (Pr) of 45 mC/m2 was obtained at maximum applied voltage of 11 V (500 MV/m) for the ultrathin film annealed at 142 °C. This Pr value is twice as high than that previously reported. We ascribed higher Pr to both smoothness of sample surface and no significant reduction of crystallinity and crystallite size when film thickness is down to 22 nm. Thermal annealing at the temperature above 135 °C induced the growth of flat-on lamella crystals with smoothed uniform surface morphology, and further thermal annealing at temperature of 142 °C led the realignment of crystal c axis in flat-on lamella parallel to the substrate.