In this work, the electrospinning technique is used for the fabrication of electrospun functional fibers with desired properties in order to show a superhydrophobic behavior. With the aim to obtain a coating with the best properties, a design of experiments (DoE) has been performed by controlling several inputs operating parameters, such as applied voltage, flow rate, and precursor polymeric concentration. In this work, the reference substrate to be coated is the aluminum alloy (60661T6), whereas the polymeric precursor is the polyvinyl chloride (PVC) which presents an intrinsic hydrophobic nature. Finally, in order to evaluate the coating morphology for the better performance, the following parameters—such as fiber diameter, surface roughness (Ra, Rq), optical properties, corrosion behavior, and wettability—have been deeply analyzed. To sum up, this is the first time that DoE has been used for the optimization of superhydrophobic or anticorrosive surfaces by using PVC precursor for the prediction of an adequate surface morphology as a function of the input operational parameters derived from electrospinning process with the aim to validate better performance.