The built‐in electric field (BEF) intensity of silicon heterojunction solar cells can be easily enhanced by selective doping to obtain high power conversion efficiencies (PCEs), while it is challenging for perovskite solar cells (pero‐SCs) because of the difficulty in doping perovskites in a controllable way. Herein, an effective method is reported to enhance the BEF of FA0.92MA0.08PbI3 perovskite by doping an organic ferroelectric material, poly(vinylidene fluoride):dabcoHReO4 (PVDF:DH) with high polarizability, that can be driven even by the BEF of the device itself. The polarization of PVDF:DH produces an additional electric field, which is maintained permanently, in a direction consistent with that of the BEF of the pero‐SC. The BEF superposition can more sufficiently drive the charge‐carrier transport and extraction, thus suppressing the nonradiative recombination occurring in the pero‐SCs. Moreover, the PVDF:DH dopant benefits the formation of a mesoporous PbI2 film, via a typical two‐step processing method, thereby promoting perovskite growth with high crystallinity and a few defects. The resulting pero‐SC shows a promising PCE of 24.23% for a 0.062 cm2 device (certified PCE of 23.45%), and a remarkable PCE of 22.69% for a 1 cm2 device, along with significantly improved moisture resistances and operational stabilities.