Ni–Mo alloy coatings were deposited on a copper base material from a non-aqueous plating bath based on a deep eutectic solvent (DES) of choline chloride and propylene glycol in a 1:2 molar ratio containing 0.2 mol dm−3 NiCl2 · 6H2O and 0.01 mol dm−3 (NH4)6Mo7O24·4H2O. Uniform and adherent Ni–Mo deposits with a nodular morphology were obtained at all the deposition potentials investigated (from − 0.5 to − 0.9 V vs. Ag). By shifting the potential from − 0.5 to − 0.9 V, the deposition current density increased from − 0.4 to − 1.5 mA cm−2 and the overall surface roughness increased. It was also accompanied by an increase in the Mo content from ~ 7 to ~ 13 wt% in the potential range from − 0.5 to − 0.7 V. A further change in the potential from − 0.8 to − 0.9 V caused a decrease in the Mo content to ~ 10 wt% and a deterioration in the quality of the coating. For the most uniform coating, deposited at − 0.6 V and having a thickness of ca. 660 nm, the crystallite size did not exceed 10 nm. With the content of Ni (89 at.%) and Mo (11 at.%), the selected area electron diffraction (SAED) analysis allowed us to identify the cubic phase Ni3.64Mo0.36. The corrosion resistance of Ni–Mo coatings in 0.05 mol dm−3 NaCl solution generally increased during exposure of 18 h, as evidenced by ever higher polarization resistance. Finally, regardless of the applied deposition potential, low corrosion currents (in the range of 0.1–0.3 μA cm−2) have been measured for the coatings. EIS revealed that charge transfer resistances were the highest (57–67 kΩ cm2) for coatings deposited at − 0.5 V, − 0.6 V and − 0.7 V. Further increase in the deposition potential in the negative direction was unfavorable.