Developing efficient and cost-effective transition metal-based electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial to generate clean and renewable hydrogen energy. The construction of hybrid catalysts with multiple active sites is an effective approach to promote catalytic performance. Herein, a molybdenum disulfide (MoS2)-based hybrid with N-doped carbon wrapped CoFe alloy (MoS2/CoFe@NC) was synthesized through a typical hydrothermal method. The MoS2/CoFe@NC exhibits excellent electrocatalytic performance with overpotentials of 172 mV for HER and 337 mV for OER at 10 mA cm−2, and long-term stability of 24-h electrolytic reaction in 1 M KOH solution. The chemical coupling between MoS2 and CoFe@NC provides improved electronic structures and more accessible active sites. The CoFe@NC substrate accelerates the charge transfer to MoS2 through a synergistic effect. This work demonstrates that the CoFe@NC is a promising substrate for depositing MoS2 nanosheets (NSs) to achieve excellent catalytic performance for both HER and OER.