The Al coatings achieved via electrodeposition on a Cu electrode from AlCl3-NaCl-KCl (80–10–10 wt.%) molten salts electrolyte with Tetramethylammonium Chloride (TMACl) and Sodium Iodide (NaI) additives is reported. The effect of the two additives on electrodeposition were investigated by cyclic voltammetry (CV), chronopotentiometry (CP), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Results reveal that compact and smooth Al coatings are obtained at 150 °C by the electrodeposition process from the electrolyte with 1% TMACl and 10% NaI. The Al coatings exhibit great corrosion resistance close to that of pure Al plate, with a corrosion current of 3.625 μA. The average particle size is approximately 2 ± 1 μm and the average thickness of the Al layer is approximately 7 ± 2 μm. The nucleation/growth process exhibits irrelevance with TMACl or NaI during the electrodeposition of Al. TMACl cannot affect and improve the electrodeposition effectively. However, the addition of TMACl and NaI can intensify the cathodic polarization, producing an inhibition of Al deposition, and contribute to form uniform Al deposits. This can increase the conductivity and facilitate in refining the size of Al particles, contributing to forming a continuous, dense and uniform layer of Al coating, which can be used as effective additives in molten salts electrolyte.