The intermetallic compounds with modulated electronic structure can provide more catalytically active sites and enhance electrocatalytic performance. In this study, the first-principles calculation method has been employed to investigate the potential of L1₀-NiM (M = Mn, Fe, Co, Cu, Zn, Mo) intermetallic compounds for electrocatalytic hydrogen evolution reaction (HER). Firstly, the L1₀-NiM present a homogenized charge transfer environment, where the Bader charge difference on the catalyst surface is below 0.13 e, significantly mitigating the locally strong adsorption of adsorbates in Ni. Additionally, the L1₀-NiM also fine-tunes the antibonding orbital interactions with adsorbates, facilitating both water dissociation and proton reduction. Furthermore, the L1₀-NiCu exhibits better HER electrocatalytic activity, with a water dissociation energy barrier of 0.49 eV and a Gibbs free energy of hydrogen adsorption of −0.524 eV. A scaling relationship analysis reveals a good linear correlation between HER activity and adsorption descriptors across the investigated L1₀-NiM intermetallic compounds, providing a theoretical foundation for the development of low-cost catalysts.