Electrolytic water splitting is a promising path for the production of clean hydrogen when combined with green electric power, such as photovoltaic and wind power; however, the high current water electrolysis is mainly dependent on the utilization of Pt, Ru, and other expensive materials, while the transition metal-based catalysts still need improvement in electrocatalytic activity and stability. Here, we present the preparation of economic and scalable electrode materials, Nickel-Iron phosphide/Nickel foam (NiFeP/NF), with a hierarchical porous structure for overall water splitting as both the anode and cathode. An overall potential of 1.85 V for the current density of 100 mA cm−2, and a long lifetime of 700 h, were achieved by using NiFeP/NF as both the anode and cathode. The nanostructures of the composite phosphides were investigated and the spent electrode after long-term electrolysis was characterized to investigate the long-term failure mechanism of the phosphides. Surface shedding and reconstruction theories were proposed for the failure of the NiFeP/NF cathode and anode in long-term electrolysis, respectively. Furthermore, TiO2 coating was proved to be an efficient strategy to elongate the lifetime of the phosphide electrodes, which shows a slow current decline rate of 0.49 mA·cm−2 h−1.