The paper considers the most significant properties of moulding solutions based on a mixture of polyvinylidene fluoride and polystyrene for the process of capillary-free electrospinning nonwoven materials. It has been shown that the material obtained from the mixed solution of polyvinylidene fluoride and polystyrene in the ratio of components 0.75 : 0.25 is the largest porous, the diameter of the fibers is in the widest range from 0.14 to 2.8 μm, and branching of the fibers is observed.