A newly designed water‐stable NH2‐MIL‐88B(Fe2Ni)‐metal–organic framework (MOF), in situ grown on the surface of a highly conducting 3D macroporous nickel foam (NF), termed NFN‐MOF/NF, is demonstrated to be a highly efficient bifunctional electrocatalyst for overall water splitting with ultrastability at high current densities. The NFN‐MOF/NF achieves ultralow overpotentials of 240 and 87 mV at current density of 10 mA cm−2 for the oxygen evolution reaction and hydrogen evolution reaction, respectively, in 1 m KOH. For the overall water splitting, it requires only an ultralow cell voltage of 1.56 V to reach the current density of 10 mA cm−2, outperforming the pairing of Pt/C on NF as the cathode and IrO2 on NF as the anode at the same catalyst loading. The stability of the NFN‐MOF/NF catalyst is also outstanding, exhibiting only a minor chronopotentiometric decay of 7.8% at 500 mA cm−2 after 30 h. The success of the present NFN‐MOF/NF catalyst is attributed to the abundant active centers, the bimetallic clusters {Fe2Ni(µ3‐O)(COO)6(H2O)3}, in the MOF, the positive coupling effect between Ni and Fe metal ions in the MOF, and synergistic effect between the MOF and NF. A metal–organic framework (MOF) based composite electrocatalyst is developed, not only retaining the unique advantageous properties but also removing the detrimental disadvantage of MOFs. The newly designed water‐stable NH2‐MIL‐88B(Fe2Ni)‐MOF, in situ grown on the surface of a highly conducting 3D macroporous nickel foam, is demonstrated to be a highly efficient bifunctional electrocatalyst for overall water splitting with ultrastability at high current densities.