In this paper, we innovatively employed low-temperature phosphorization technology to successfully incorporate P doping into NiMoO4 nanorods. Subsequently, utilizing the electrodeposition method with a solution rich in Ni²⁺ and Fe³⁺ as the electrolyte, we delicately tuned the process to identify the optimal deposition time, achieving a uniform coating of NiFe LDH on the surface of the P-doped NiMoO4 nanorods. This led to the construction of a three-dimensional core-shell structured NiFe LDH@P-NiMoO4 composite material. To validate the performance of this composite, we conducted thorough structural characterization and electrochemical oxygen evolution reaction (OER) performance tests. The experimental results revealed that in a 1 M KOH electrolyte environment, when the current density reached 100 mA cm⁻², the composite exhibited exceptionally superior OER performance, with an overpotential of merely 267 mV and a Tafel slope as low as 93 mV dec⁻¹, firmly demonstrating its remarkable catalytic efficiency. Furthermore, the composite displayed good stability and durability during prolonged testing, providing a solid foundation for its practical application. In summary, this work not only paves a new way for the preparation of high-performance non-precious metal OER electrocatalysts but also provides robust support for the realization of efficient and stable energy conversion and storage technologies.