The design of highly efficient electrocatalysts containing non-precious metals is crucial for promoting overall water splitting in alkaline media. In particular, Janus catalysts simultaneously facilitating the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are desirable. Herein, we fabricated a unique hierarchical heterostructure via growing Ni4W6O21(OH)2·4H2O (denoted as Ni-W-O) nanosheets on NiMoO4 rods, which was indispensable for regulating the morphology of the Ni-W-O structure. This heterostructure of Ni-W-O/NiMoO4 could be utilized as an electrocatalyst to realize superior activity for overall water splitting in 1.0 M KOH. It substantially promoted overall water splitting with 1.6 V at 30 mA cm-2, outperforming numerous bifunctional electrocatalysts under the same conditions. Notably, the remarkable stability for continuously splitting water endowed this hierarchical heterostructure with potential applications on a large scale. This work emphasizes the effectively controlled growth of heterostructured non-noble-metal catalysts for energy-conversion reaction.