The sluggish kinetics and issues associated with the parasitic reactions of cathodes are major obstacles to the large‐scale application of Li–O2 batteries (LOBs), despite their large theoretical energy density. Therefore, efficient electrocatalyst design is critical for optimizing their performance. Ni5P4 is analyzed theoretically as a cathode material, and the downshift of the d‐band center is found to enhance electron occupation in antibonding orbits, providing a valuable descriptor for understanding and enhancing the intrinsic electrocatalytic activity. In this study, it is demonstrated that incorporating additional nitrogen atoms into Ni5P4 nanoroses regulates the electronic structure, resulting in superior electrocatalytic performance in LOBs. Further spectroscopic analysis and density functional theory calculations reveal that the incorporated nitrogen sites can effectively induce localized structure polarization, lowering the energy barrier for the production of desirable intermediates and thus enhancing battery capacity and preventing cell degradation. This approach provides a sound basis for developing advanced electrode materials with optimized electronic structures for high‐performance LOBs.

The remarkably high theoretical energy densities of Li-O2 batteries have triggered tremendous efforts for next-generation conversion devices. Discovering efficient ORR/OER bifunctional catalysts and revealing their internal structure-property relationships are crucial in developing high-performance Li-O2 batteries. Herein, we have prepared a nanoflower-like Ni5P4@NiSe2 heterostructure and employed it as a cathode catalyst for Li-O2 batteries. As expected, the three-dimensional biphasic Ni5P4@NiSe2 nanoflowers facilitated the exposure of adequate active moieties and provide sufficient space to store more discharge products. Moreover, the strong electron redistribution between Ni5P4 and NiSe2 heterojunctions could result in the built-in electric fields, thus greatly facilitating the ORR/OER kinetics. Based on the above merits, the Ni5P4@NiSe2 heterostructure catalyst improved the catalytic performance of Li-O2 batteries and holds great promise in realizing their practical applications as well as inspiration for the design of other catalytic materials.