Developing low-cost, high-performance and corrosion-resistant catalysts for water splitting is anticipated, but it will also be a big challenge. In this study, nanowall-like N-Ni₅P₄/Ni₂P/NF (N-NiP/NF) was synthesized by a simple two-step method involving hydrothermal treatment and phosphorylation. The catalyst has good catalytic activity for the OER, and only 160 mV is required to achieve a current density of 10 mA cm⁻² in 1 M KOH, which is even better than RuO₂, with good corrosion resistance. In addition, N-Co₂P/Ni₂P/NF (N-CoP/NF) was synthesized by the same method with good electrocatalytic properties and good conductivity towards the HER. N-NiP/NF was used as the anode and N-CoP/NF was used as the cathode to form the N-NiP//N-CoP double electrode system, which showed excellent electrolytic performance for water splitting, requiring only 1.48 V to reach 10 mA cm⁻². This is mainly due to the strong electronegativity of N that makes the N doping induce the electron transfer process, which results in a high catalytic activity of the adjacent transition metal atoms and thus promotes the electrolysis of water, as well as the unique vertical nanowall-like structure, which gives the material a large surface area and accessibility to active sites, facilitating the adsorption of water molecules and catalytic reactions. In addition, the unique structure favors the diffusion of water molecules and the release of gaseous products, ensuring close contact between the catalyst and the electroactive material. This simple non-metallic N doping strategy provides a new way to produce efficient non-precious metal catalysts.