The rational design of the interfacial electrocatalyst heterostructure MoS2 is guided by the kinetics investigation. By optimizing the electronic structure based on the simultaneous modulation of the 3d‐band‐offsets of Ni, Co, and Mo near the interface, superior pH‐universal hydrogen evolution performances are achieved, which opens up a new strategy in the design of highly efficient electrocatalysts. Abstract As a prerequisite for a sustainable energy economy in the future, designing earth‐abundant MoS2 catalysts with a comparable hydrogen evolution catalytic performance in both acidic and alkaline environments is still an urgent challenge. Decreasing the energy barriers could enhance the catalysts’ activity but is not often a strategy for doing so. Here, the first kinetic‐oriented design of the MoS2‐based heterostructure is presented for pH‐universal hydrogen evolution catalysis by optimizing the electronic structure based on the simultaneous modulation of the 3d‐band‐offsets of Ni, Co, and Mo near the interface. Benefiting from this desirable electronic structure, the obtained MoS2/CoNi2S4 catalyst achieves an ultralow overpotential of 78 and 81 mV at 10 mA cm−2, and turnover frequency as high as 2.7 and 1.7 s−1 at the overpotential of 200 mV in alkaline and acidic media, respectively. The MoS2/CoNi2S4 catalyst represents one of the best hydrogen evolution reaction performing ones among MoS2‐based catalysts reported to date in both alkaline and acidic environments, and equally important is the remarkable long‐term stability with negligible activity loss after maintaining at 10 mA cm−2 for 48 h in both acid and base. This work highlights the potential to deeply understand and

Published in: "Advanced Functional Materials".