Developing noble‐metal‐free, earth‐abundant, highly active, and stable electrocatalysts with high efficiency for both hydrogen and oxygen evolution reactions is of great importance for the development of overall water‐splitting devices, but still remains a challenging issue. Herein, a 3D heterostructured NiC/MoC/NiMoO4 electrocatalyst was prepared through a facile synthetic procedure. The electrocatalyst shows a superior catalytic activity and stability toward the hydrogen and oxygen evolution reactions. The optimized NiC/MoC/NiMoO4 catalyst presents low overpotentials of 68 and 280 mV to reach a current density of 10 mA cm−2 in 1.0 m KOH for the hydrogen and oxygen evolution reactions, respectively. Assembled as an electrolyzer for overall water splitting, such a heterostructure shows quite a low cell voltage of 1.52 V at 10 mA cm−2 and remarkable stability for more than 20 h. This work provides a facile but efficient approach for the design and preparation of highly efficient bifunctional and self‐supported heterostructured electrocatalysts that can serve as promising candidates in electrochemical energy storage and conversion.