In this study, the pristine MgO, MgO/CNT and Ni-MgO/CNT nanocomposites were processed using the impregnation and chemical vapor deposition methods and analyzed for hydrogen evolution reaction (HER) using the electrochemical water splitting process. Furthermore, the effect of nickel on the deposited carbon was systematically elaborated in this study. The highly conductive carbon nanotubes (CNTs) deposited on the metal surface of the Ni-MgO nanocomposite heterostructure provides a robust stability and superior electrocatalytic activity. The optimized Ni-MgO/CNT nanocomposite exhibited hierarchical, helical-shaped carbon nanotubes adorned on the surface of the Ni-MgO flakes, forming a hybrid metal–carbon network structure. The catalytic HER was carried out in a 1M alkaline KOH electrolyte, and the optimized Ni-MgO/CNT nanocomposite achieved a low (117 mV) overpotential value (ɳ) at 10 mA cm−2 and needed a low (116 mV/dec) Tafel value, denotes the Volmer–Heyrovsky pathway. Also, the high electrochemical active surface area (ECSA) value of the Ni-MgO/CNT nanocomposite attained 515 cm2, which is favorable for the generation of abundant electroactive species, and the prepared electrocatalyst durability was also performed using a chronoamperometry test for the prolonged duration of 20 h at 10 mA cm−2 and exhibited good stability, with a 72% retention. Hence, the obtained results demonstrate that the optimized Ni-MgO/CNT nanocomposite is a highly active and cost-effective electrocatalyst for hydrogen energy production.