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• Self-supporting ternary alloy catalyst was prepared by one step growth. • The principle of interface reaction at the atomic level. • Excellent HER properties attributed to ternary alloy catalysts structure. Active electrocatalysts are the key of water splitting for hydrogen production through the electrolysis. In this paper, Ni foams substrates as templates, self-supporting ternary alloy catalyst was prepared by one step at room temperature. Growth mechanism of self-supporting ternary alloy catalyst is explored by growth process. Micro-current technology of galvanic reaction and the principle of interface electric double layer reaction are important to the self-supporting ternary alloy catalyst. Their catalytic activity was evaluated by electrocatalytic hydrogen evolution(HER). It exhibits excellent HER properties with a overpotential (17 mV) and small Tafel slope (10.2 mVdec−1). Their enhanced performances in HER catalysts can be mainly attributed to ternary alloy catalysts structure, which allows the appearance synergistic effects and larger specific surface area. This research is to control the micro-area of chemical reaction at the atomic level by non-precious template and all kinds of precursor mixture solution. Self-supporting ternary alloy catalyst was prepared by one-step galvanic replacement. They display exerlent superior activity for the HER in base solution with an onset reduction potential of + 17 mV vs RHE and small Tafel slope (10.2 mVdec−1). This activity is due to the synergistic effects and larger specific surface area. [Display omitted]. [ABSTRACT FROM AUTHOR]