Abstract The 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 Co 3 O 4 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.