Ferroclectric materials have been extensively studies in the past decades because they pave the way to a myriad of electrically controlled devices including nonvolatile ferroelectric random access memories, sensors and actuators.Among ferroelectric materials, ferroelectric polymers such as poly(vinylidene fluoride) and its copolymers with trifluoroethylene (P(VDF-TrFE) are especially attractive owing to their high flexibility, low cost, and stackability of a series of active memory layers.Elucidating the structure-property relationship would, thus, not only provide an understanding of the fundamental features of ferroelectric polymers, but also lead to a more rational optimization of ferroelectric devices.