AbstractAs the most important layered transition metal dichalcogenide, molybdenum disulfide (MoS2) is applicable for simultaneous H2 production and CO elimination by water‐gas shift reaction (WGSR), while its performance is still not satisfactory. To further promote the catalytic activities of MoS2, herein a series of transition metals (M = Mn, Fe, Co, Ni, Cu, and Zn) into the column‐like superstructures with edge‐terminated MoS2 nanosheet building blocks (termed as M‐ET MoS2 SSs) is doped as the efficient catalysts for WGSR. A precise M doping into ET MoS2 SSs reveals that the M‐ET MoS2 SSs exhibit the volcano‐like activity toward WGSR as a function of specific M with the 5%Ni‐ET MoS2 SSs displaying the best average rate of 50.48 µmolH2 gcat. −1 s−1 in WGSR at 473 K, which is 4 and 13 times higher than those of the ET MoS2 SSs and commercial MoS2, respectively, and is even comparable to many noble‐metal‐based catalysts. The valence band spectra reveal that the boosted WGSR activity of 5%Ni‐ET MoS2 SSs can be ascribed to the downshift of the d‐band center relative to the Fermi level, which facilitates the H desorption to produce H2 in WGSR, showing a highly efficient and earth‐abundant catalysts for WGSR and beyond.