In the fluoropolymers family, one of the newest members is the terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV). There are scarce data on THV, and therefore it is necessary to study different properties of THV. In the current research, the detailed surface morphology and water wettability of electrospun microfibers prepared from THV/ethyl acetate solutions in the pure state and with the addition of Wyoming-type low-magnesium montmorillonite are discussed. The morphology of the terpolymer microfibers changes as a function of the polymer solution concentration. For the same polymer concentration, changing the applied voltage in microfiber formation does not alter the morphology. The addition of hydrophilic montmorillonite into the THV solution does not modify the rougher hydrophobic nature and morphology of the final electrospun fiber surfaces. Water contact angle measurements show that both in the pure state and in the mixture of montmorillonite, THV electrospun microfibers exhibit near superhydrophobic characteristics with contact angles as high as 145 degrees.