Abstract: | Hierarchical nanostructures with tailored component and architectures are attractive for energy‐related applications. Here, the delicate design and construction of hierarchical MoS2/MoP (H‐MoS2/MoP) nanorods for the hydrogen evolution reaction (HER) are demonstrated. This multiscale design rationally combines the compositional and structural advantages of MoS2/MoP heterojunction into a hierarchical architecture, which can modulate electronic structure of S, remarkably facilitating the electrocatalytic HER. Benefitting from their unique architecture and electronic structure, the H‐MoS2/MoP nanorods exhibit excellent performance for HER with ultralow overpotential of 92 mV at current density of 10 mA cm?2 in 1 m KOH and high stability. This work not only provides an efficient approach to constructing hierarchical heterojunctions, but also a multiscale strategy for all‐round regulation of the electronic structure and hierarchical morphology of nanomaterials for energy‐related applications. |