The ingenious design and synthesis of bifunctional electrocatalysts with high activity and robust stability for hydrogen evolution reaction and oxygen evolution reaction (HER and OER) is desirable and challenging. Herein, bimetallic phosphides CoFeP with hollow microspheres structure has been synthesized through a facile gas phosphorization as bifunctional electrocatalyst for overall water splitting. SEM and TEM demonstrate the formation of uniform hollow microspheres of CoFeP. The hollow structure of CoFeP is helpful to increase the exposed actives and the larger contact surface with electrolyte. The bimetallic composites can provide the better intrinsic activity. Compared with single metallic phosphides CoP and FeP, the obvious enhancement of electrocatalytic performances of CoFeP can be observed. The electrochemical results show that the bimetallic CoFeP hollow microspheres only have the lower overpotential of 177 and 350 mV (vs. RHE) to drive a current density of 10 mA cm(-2) for HER and OER, respectively. The reasons may be due to the hollow nanostructure and the synergistic effect from bimetallic phosphides. This work provides a facile and effective way to design excellent phosphides electrocatalysts for water splitting based on gas phosphorization of bimetallic oxides precursors.