Inducing the formation of stable bonding states on the surface of the catalyst is one of the significant ways to improve the photocatalytic activity of the semiconductor. The design and construction of stable bonding states on the surface of catalysts by a one-step oxidation-phosphorus doping tactics has not been reported in the field of photocatalysis. In this work, P(δ–)-Co/Ni(δ+)-O(δ–) surface bonding state was built and design on the surface of Nickel-cobalt layered double hydroxids (NiCo-LDH) nanoflowers via a one-step oxidation-phosphorus doping strategy. The formation of surface bonding states can efficient capture photoproduction electrons, thus stopping the reassociation of NiCo2O4 photogenerated carriers and greatly improving the photocatalytic hydrogen evolution liveness of NiCo2O4, and the hydrogen evolution amount of 0.3P-NCO was 7.45 times and 2.38 times that of NiCo-LDH and NiCo2O4 within 5 h, respectively. In addition, the construction of surface bonding states can improve the durability and stability of 0.3P-NCO. This work offers a strategy for surface-induced engineering design and highlights the critical role of surface-bonding states in novel photocatalysts and photocatalytic hydrogen production processes.