In this study, CoFe bimetallic phosphide microflowers electrocatalyst are supported on nickel foam. The bimetallic composition and phosphating can effectively improve the OER and HER performances and realize optimized overall water splitting performance. It requires only an overpotential of 68 mV in 1 M KOH to reach a current density of 10 mA·cm−2 for HER and only 227 mV for OER. When optimal sample (CoFe10%-P/NF) was used for overall water splitting, a low cell voltage of 1.610 V is required at 10 mA·cm−2 in alkaline solution. The stability was also good. This study provides feasible proposals for overall water splitting.