This work investigates the structural and electrophysical properties of films of vinylidene fluoride-tetrafluoroethylene copolymer (VDF/TFE) derived from xerogel. Materials produced in this manner have a porous structure with unique properties. The high values of pyroelectric and piezoelectric response, as well as the chemical and thermal stability of VDF/TFE, make the polymer promising for various engineering applications, including flexible electronics materials, particularly for creating sensors, actuators, and energy storage devices. Films made from the melt or solution using traditional methods require subsequent processing to acquire ferroelectric properties, such as stretching, isothermal annealing, and polarization. The production of films from xerogel can potentially reduce the technological process of creating ferroelectric materials with an ordered structure. It has been shown that VDF/TFE xerogel films possess sufficient crystallinity, an ordered structure, and high lateral piezoelectric response values. © 2024 IEEE.