The invention belongs to the technical field of electronic materials and devices, and particularly relates to a method for preparing highly oriented Poly(vinylidene fluoride-trifluoroethylene) copolymer film. The method is based on a removable polytetrafluoroethylene ordered mold plate, and comprises the following steps of tightly pressing a PTFE mold plate on a ferroelectric polymer film within a specific temperature range(149-330 DEG C), wherein the exerted pressure intensity range is 0.5-10MPa; and the duration of the pressure intensity is at least 10 minutes; and then after the temperature is reduced to room temperature, removing the pressure intensity, and peeling off the PTFE mold plate, so that the highly ordered epitaxially grown ferroelectric polymer film can be obtained. Through the adoption of the method disclosed by the invention, the preparation of the ferroelectric film which is low in electric leakage and high in ferroelectric performance is realized, so that the ferroelectric films can be applied to ferroelectric electronic devices which are low in power dissipation and low in requirement for working voltage.