Among the various polymeric options employed for the deposition of electrospun coatings, poly(vinylidene fluoride) (PVDF) has been widely investigated thanks to its excellent mechanical properties, high chemical resistance, and good thermal stability. In this work, the electrospinning technique is used for the fabrication of functional PVDF fibers in order to identify and evaluate the influence of the experimental conditions on the nanofiber properties in terms of optical transmittance, wettability, corrosion resistance, and surface morphology. Some of these properties can play a relevant role in the prevention of ice formation in aircrafts. According to this, a matrix of 4 × 4 samples of aluminum alloy AA 6061T6 was successfully coated by controlling two operational input parameters such as the resultant applied voltage (from 10 up to 17.5 KV) and the flow rate (from 800 up to 1400 µL/h) for a fixed polymeric precursor concentration (15 wt.%). The experimental results have shown a multilevel fiber-bead structure where the formation of a fiber mesh directly depends on the selected operational parameters. Several microscopy and surface analysis techniques such as confocal microscopy (CM), field emission scanning electron microscopy (FE-SEM), UV/vis spectroscopy, and water contact angle (WCA) were carried out in order to corroborate the morphology, transmittance, and hydrophobicity of the electrospun fiber composite. Finally, the corrosion behavior was also evaluated by electrochemical tests (Tafel curves measurement), showing that the presence of electrospun PVDF fibers produces a relevant improvement in the resultant corrosion resistance of the coated aluminum alloys.