It is of significance to design of stable and cost-effective electrocatalyst for water splitting with high efficiency in an alkaline medium. The major obstacles for practical application of water splitting devices are lack of high-efficiency and low-cost electrocatalysts with low overpotential for both HER and OER. In this paper, we report a NiFe alloy decorated NiCoO2 hollow polyhedron (denoted as NiFe –NiCoO2 ) by using [NiFe(CN) 6 ] intercalated NiCo –LDH as precursor. As evidenced by the electrochemical active surface area, the resultant NiFe –NiCoO2 composite shows unique hollow nanostructure, which can not only provide abundant mass transport channels, but also increase the contact area of the NiFe –NiCoO2 material with the electrolyte. The overpotential ( η) demand iS286 mV for OER and 102 mV for HER at the current density of 10 mA/cm 2 in an alkaline medium of 1 M KOH for the NiFe/NiCoO2 composite. This work provides a new pathway for preparation of the highly efficient bifunctional electrocatalysts for water splitting.