Water electrolysis shows great promise for the low-cost mass production of high-purity hydrogen. The relatively high dissociation energy of water, however, often results in rather sluggish kinetics of the hydrogen evolution reaction (HER) in alkaline conditions, even for the case of state-of-the-art Pt-based electrocatalysts. Here, we show the high efficiency of the hybrids of PtRu nanoclusters (NCs) and black phosphorus (BP) nanosheets in HER. Our PtRu NCs/BP electrocatalysts demonstrate a HER activity of 88.5 mA cm–2 at −70 mV in 1 M KOH, which is higher than that of commercial Pt/C by 1 order of magnitude. The observed extraordinarily high HER activity of the PtRu NCs/BP hybrids is interpreted in the framework of density functional theory. Theoretical modeling indicates that the electronic interaction between BP and PtRu NCs speeds up the dissociation of water and optimizes the adsorption strength for H* species, giving rise to the remarkably high HER activity of the PtRu NCs/BP hybrids.