The exploration of low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) is a prerequisite for large-scale hydrogen fuel generation. The understanding of the electronic properties of electrocatalysts plays a key role in this exploration process. In this study, our first-principles results demonstrate that the catalytic performance of the 1D metal–organic frameworks (MOFs) can be significantly influenced by engineering the composite of the metal node. Using the Gibbs free energy of the adsorption of hydrogen atoms as a key descriptor, we found that Ni- and Cr-based dithiolene MOFs possess better hydrogen evolution performance, and the much different efficiencies can be ascribed to their electronic resonance structures [TM3+(L2–)(L2–)]− ↔ [TM2+(L•–)(L2–)]−. The [TM2+(L•–)(L2–)]− structure is preferred due to the higher activity of the catalytic site L with more radical features, and the stabilized [TM2+(L•–)(L2–)]− structure of the Cr- and Ni-based MOFs can be ascribed to the electronic configurations of their TM2+ cations with half-occupied and fully occupied valence orbitals. Our results therefore reveal a novel strategy for optimizing the electronic structures of materials on the basis of the resonant charge-transfer mechanism for their practical applications.