AbstractThe exploitation of highly activity oxygen evolution reaction (OER) electrocatalysts is critical for the application of electrocatalytic water splitting. Triggering the lattice oxygen mechanism (LOM) is expected to provide a promising pathway to overcome the sluggish OER kinetics, however, effectively enhancing the involvement of lattice oxygen remains challenging. In this study, the fabrication of B, Fe co‐doped CoP (B, Fe─CoP) nanofibers is reported, which serve as highly efficient OER electrocatalyst through phosphorization and boronation treatment of Fe‐doped Co3O4 nanofibers. Experimental results combined with theoretical calculations reveal that simultaneous incorporation of both B and Fe can more effectively trigger the participation of lattice oxygen in CoFe oxyhydroxides reconstructed from B, Fe─CoP nanofibers compared to incorporating only B or Fe. Therefore, the optimized B, Fe─CoP nanofibers exhibit superb OER activity with low overpotentials of 361 and 376 mV at 1000 mA cm−2 in alkaline freshwater and alkaline natural seawater, respectively. The present work provides significant guidelines and innovative design concepts for the development of OER electrocatalysts following the LOM pathway.