The ferroelectric material of BaTiO3 was introduced in the electron transport layer (ETL) of perovskite solar cells to improve the photogenerated electron transport. The sintered BaTiO3 thin films were polarized at different applied electric fields, and then TiO2 thin films were further deposited to be used as the ETL. The electric field was positively applied across the BaTiO3 thin film, and the photocurrent density of solar cell can be increased obviously. The results of electrochemical impedance and photoluminescence spectra indicate that the ordered polarization dipole moment inside the BaTiO3 thin film can accelerate the transport of photogenerated electrons from the ETL to the conducting glass substrate. The short-circuit photocurrent of perovskite solar cell is increased and thus the light-to-electric conversion efficiency is effectively improved to 13%. It is increased by 14% compared with that without the application of the positive electric field across the BaTiO3 thin film.