Wound healing of the oral mucosa is an urgent problem in modern dental surgical practice. This research article presents and compares the findings of the investigations of the structural, physicochemical, and biological characteristics of two types of polymeric membranes used for the regeneration of oral mucosa. The membranes were prepared from poly-(tetrafluoroethylene) (PTFE) and a copolymer of vinylidene fluoride and tetrafluoroethylene (VDF-TeFE) and analyzed via scanning electron microscopy, atomic force microscopy, X-ray diffraction analysis, and Fourier transform infrared spectroscopy. Investigation results obtained indicate that both types of membranes are composed of thin fibers: (0.57 ± 0.25) μm for PTFE membranes and (0.43 ± 0.14) μm for VDF-TeFE membranes. Moreover, the fibers of VDF-TeFE membranes exhibit distinct piezoelectric properties, which are confirmed by piezoresponse force microscopy and X-ray diffraction. Both types of membranes are hydrophobic: (139.7 ± 2.5)°for PTFE membranes and (133.5 ± 2.0)°for VDF-TeFE membranes. In vitro assays verify that both membrane types did not affect the growth and division of mice fibroblasts of the 3T3-L1 cell line, with a cell viability in the range of 88−101%. Finally, in vivo comparative experiments carried out using Wistar rats demonstrate that the piezoelectric VDF-TeFE membranes have a high ability to regenerate oral mucosa.