The production of hydrogen through seawater electrolysis has recently garnered increasing concern. However, hydrogen evolution reaction (HER) by alkaline seawater electrocatalysis is severely impeded by the slow H2O adsorption and H* binding kinetics at industrial current densities. Herein, a face-centered cubic/hexagonal close packed (fcc/hcp) NiRu alloy heterojunction was fabricated on Ni foam (N doped NiRu-inf/NF) by a low-temperature nitrogen plasma activation. Simultaneously, nitrogen atoms are introduced into the alloy to facilitate d-p hybridization. When N doped NiRu-inf/NF is integrated into a dual-electrode cell for urea-assisted seawater electrolysis, it achieves 100 mA cm−2 with an ultra-low voltage of 1.36 V and excellent stability. Density functional theory (DFT) verifies that the robust d-p hybridization among Ni, Ru and N exhibits more energy level matching for H2O molecule adsorption at the Ru sites, while simultaneously reducing the interaction between H* and Ni sites in N-doped NiRu-inf.