Binary metallic nickel–copper nanocatalysts were anchored onto a polyvinylidene fluoride-co-hexafluoropropylene membrane [NiCu/PVdF–HFP] using the electrospinning technique, followed by the chemical reduction of the relevant precursor salts by introducing sodium borohydride to the synthesis mixture. A series of varied Ni:Cu weight % proportions was developed in order to optimize the electroactivity of this binary nanocomposite towards the investigated oxidation process. A number of physicochemical tools were used to ascertain the morphology and chemical structure of the formed metallic species on polymeric films. Cyclic voltammetric studies revealed a satisfactory performance of altered NiCu/PVdF–HFP membranes in alkaline solution. Ethylene glycol molecules were successfully electro-oxidized at their surfaces, showing the highest current intensity [564.88 μA cm−2] at the one with Ni:Cu weight ratios of 5:5. The dependence of these metallic membranes’ behavior on the added alcohol concentration to the reaction electrolyte and the adjusted scan rate during the electrochemical measurement was carefully investigated. One hundred repeated scans did not significantly deteriorate the NiCu/PVdF–HFP nanostructures’ durability. Decay percentages of 76.90–87.95% were monitored at their surfaces, supporting the stabilized performance for prolonged periods. A much-decreased Rct value was estimated at Ni5Cu5/PVdF–HFP [392.6 Ohm cm2] as a consequence of the feasibility of the electron transfer step for the electro-catalyzing oxidation process of alcohol molecules. These enhanced study results will hopefully motivate the interested workers to explore the behavior of many binary and ternary combinations of metallic nanomaterials after their deposition onto convenient polymeric films for vital electrochemical reactions.