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Design and synthesis of non-precious-metal catalyst for efficient electrochemical transformation of water to molecular hydrogen in acid environments is of paramount importance in reducing energy losses during the water splitting process. Here, the hybrid material of MoS 2 -coated Cu loaded on the multi-walled carbon nanotubes (MWCNTs@Cu@MoS 2 ) was synthesized using chemical process and hydrothermal method. It was found that the participation of MWCNTs and Cu nanoparticles not only improved the electrical conductivity of the catalyst, but also further enhanced the catalytic activity by synergistic effect with edge-exposed MoS 2 -coating. Electrochemical experiments demonstrated that the catalyst exhibited excellent hydrogen evolution reaction (HER) activity with large cathode currents (small overpotential of 184 mV for 10 mA cm −2 current density) and a Tafel slope as small as 62 mV per decade. Furthermore, it was discovered that the current density of this composite catalyst had a little decrease after the continual 1000 cycling, which showed the catalyst had a high stability in the recycling process. These findings confirmed that this catalyst was a useful and earth-abundant material for water splitting. [ABSTRACT FROM AUTHOR]