Highly active, stable and low-cost noble metal-free electrocatalysts are essential for production of hydrogen. However, preparation of such catalysts is still highly challenging so far. In this work, the Mo2C– carbon nanomaterials have been prepared by controlled thermal technique. By controlling concentration of the reactants in the experimental condition, the Mo2C– carbon nanomaterials have been fabricated, which leads to decreases in contact resistance b/w Mo2C– carbon nanomaterials and graphitic carbon atoms. As a result, the Mo2C– carbon nanomaterial electrode shows remarkable activity for hydrogen evolution reactions with a small onset overpotential of 95 mV, a Tafel slope of 62 mV dec−1, an high exchange current density of 0.32 mA cm−2, good stability during long-term 1000 cycles and exhibits long-term durability for several days. This study opens a new method for the preparation of highly active non-noble electrode for production of hydrogen from water splitting.