Developing low-cost and high-efficiency nonprecious electrocatalysts for the hydrogen evolution reaction (HER) to replace platinum (Pt)-based electrocatalysts is highly desirable for industrial water electrolysis. Nevertheless, the rational design and facile fabrication of an efficient nonprecious HER electrocatalyst is still a huge challenge. Herein, a series of nickel/carbon materials (Ni@C) nanocomposites have been successfully prepared and characterized. In the synthesis of Ni@C samples, the good conductivity of carbon materials can accelerate interfacial charge transfer and thus promote electrocatalytic HER performance, while the component ratio between Ni and C can be adjusted by tuning the mass of carbon precursor. Among all Ni@C samples, the as-prepared Ni@C-0.8 exhibits excellent electrocatalytic HER performance and long-time stability in an alkaline electrolyte. The optimized Ni@C-0.8 exhibits outstanding electrocatalytic HER performance with a low overpotential of 134 mV at the current density of −10 mA cm⁻² and good durability. The superior electrocatalytic HER performance of the Ni@C-0.8 sample originates from the large specific surface area and mesoporous structure of C materials. This research offers a new approach for fabricating and developing economical and efficient transitional metal-based HER electrocatalysts for potential industrial water splitting.