The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). A self-supporting, multiscale porous NiFeZn/NiZn-Ni catalyst with a triple interface heterojunction on nickel foam (NF) (NiFeZn/NiZn-Ni/NF) was in-situ fabricated using an electroplating-annealing-etching strategy. The unique multi- interface engineering and three-dimensional porous scaffold significantly modify the mass transport and electron interaction, resulting in superior bifunctional electrocatalytic performance for water splitting. The NiFeZn/NiZn-Ni/NF catalyst demonstrates low overpotentials of 187 mV for HER and 320 mV for OER at a current density of 600 mA/cm2, along with high durability over 150 h in alkaline solution. Furthermore, an electrolytic cell assembled with NiFeZn/NiZn-Ni/NF as both the cathode and anode achieves the current densities of 600 and 1000 mA/cm² at cell voltages of 1.796 and 1.901 V, respectively, maintaining the high stability at 50 mA/cm² for over 100 h. These findings highlight the potential of NiFeZn/NiZn-Ni/NF as a cost-effective and highly efficient bifunctional electrocatalyst for overall water splitting.