A Mo–Ni alloy has been demonstrated to be a benchmark noble-metal-free catalyst for the hydrogen evolution reaction (HER) in alkaline solutions. Nevertheless, further improvement on its catalytic activity is desired to meet industrial requirements. In this study, Mo–Ni-based hollow structures (MoNi-HS), backboned by MoO_3–x nanosheets and decorated with metallic MoNi₄ nanoparticles, were obtained via a topological transformation process by annealing MoNi-oxide hollow precursors in a reducing atmosphere. This hollow structure allowed for a large proportion of catalytic surface exposed in the electrolyte, leading to highly efficient utilization of active sites in the catalyst. As a result, robust catalytic activity toward HER was recorded in 1 M KOH electrolyte: a low overpotential of 38 mV to deliver a current density of 10 mA/cm² and a very small Tafel slope of 31.4 mV per dec. Such a remarkable performance of MoNi-HS even outperformed the catalytic activity of the commercial Pt/C electrocatalyst, addressing an effective strategy to promote the catalytic performance of noble-metal-free catalysts.