Molybdenum carbide is a cost‐effective alternative to Pt‐group noble metal electrocatalyst for hydrogen evolution reaction (HER), developing a facile strategy to improve the HER activity of molybdenum carbide and understanding the mechanism is of great concern and challenging. Herein, a solvothermal‐assisted self‐assembly procedure of fabricating sandwiched NiO/β‐Mo2C/RGO nanocomposite catalyst was reported. Electrochemical measurements demonstrate that the catalytic activity and durability of β‐Mo2C can be significantly improved in the sandwiched NiO/β‐Mo2C/RGO. Comparative studies between various catalysts such as β‐Mo2C, NiO/β‐Mo2C, β‐Mo2C/RGO, and NiO/β‐Mo2C/RGO have been performed to explore the mechanism underpinning their different catalytic performance. Our results revealed that hybrid of β‐Mo2C and RGO resulted in significant improvement in electrical conductivity, NiO loading modified the electron density on the surface of β‐Mo2C (101) to the electron‐rich state to generate highly active catalytic site. The synergistic effect of RGO and NiO loading would be responsible for the improved electrocatalytic performance of the NiO/β‐Mo2C/RGO catalysts. The strategy developed in this work not only provides a new pathway for improving HER activity of molybdenum carbide but also deepens fundamental understandings on the structure‐reactivity of molybdenum carbide‐based nanocomposite catalysts with higher HER activity.
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