Exploring efficient catalysts for alkaline seawater electrolysis is highly desired yet challenging. Herein, coupling single-atom rhodium with amorphous nickel hydroxide nanoparticles on copper nanowire arrays is designed as a new active catalyst for the highly efficient alkaline seawater electrolysis. We found that an amorphous Ni(OH)2 nanoparticle is an effective catalyst to accelerate the water dissociation step. In contrast, the single-atom rhodium is an active site for adsorbed hydrogen recombination to generate H2. The NiRh-Cu NA/CF catalyst shows superior electrocatalytic activity toward HER, surpassing a benchmark Pt@C. In detail, the NiRh-Cu NA/CF catalyst exhibits HER overpotentials as low as 12 and 21 mV with a current density of 10 mA cm-2 in fresh water and seawater, respectively. At high current density, the NiRh-Cu NA/CF catalyst also exhibits an outstanding performance, where 300 mA cm-2 can be obtained at an overpotential of 155 mV and shows a slight fluctuation in the current density over 30 h.