Non-precious metal-based electrocatalyst with high activity and stability for efficient hydrogen evolution reaction (HER) is of critical importance toward low-cost and large-scale water splitting. Traditional MoS2 has electrocatalytic hydrogen evolution inertness in alkaline environment, which is detrimental to the adsorption and dissociation of water. Composited with electrocatalyst with good electrical conductivity can enhance its HER activity. In this work, we for the first time construct a carbon-supported hollow heterostructure MoS2@Mo2C composite via two-step calcination and sulfurized process from carbonized Mo2C-Mo3C2 heteronanowires. The results show that the existence of the Mo3C2 phase is the key point to construct the effective heterostructure with hollow morphology. Due to the strong negative hydrogen binding energy for H on surface of Mo2C, the H+ reduction in the MoS2@Mo2C in the Volmer step can be enhanced. Compared with MoS2, MoS2@Mo2C has high electrocatalytic activity for hydrogen evolution with an onset potential of 28 mV, overpotential of 129 mV at the current density of 10 mA cm(-2), a small Tafel slope of 78 mV dec(-1), and an excellent stability. This work will provide new insights into the design of high-efficiency HER catalysts via interfacial engineering at nanoscale for commercial water splitting.