A multilayered composite that expanded the applications of electrospun fluoroplastic F-42 membranes was described. The supporting substrate was thermally bonded to the functional fluoroplastic membrane by a layer of nitrile-butadiene rubber and a transitional fibrous layer of a fluoroplastic-rubber mixture. A solvent system was selected after the thermodynamic quality of spinning solutions based on F-42/SKN-26 was studied. The physicomechanical and thermophysical characteristics of the functional composite layers were investigated.