Developing efficient, nonprecious, and durable electrocatalysts with favorable nanostructures is a persistent challenge yet significant for hydrogen evolution reaction (HER). Herein, for the first time, we report a rationally designed strategy for the synthesis of hierarchical hollow MoP nanospheres anchored on N, P, S co-doped porous carbon (hs-MoP/NPSC). Importantly, the porous shell of hollow nanosphere is actually well constructed by numbers of interwoven MoP subunits, which is beneficial for exposing of surface active sites as much as possible and promoting the mass transport during the HER process. In addition, the heteroatom-enriched porous carbon networks can further reduce the electron/ion transfer resistance. As expected, the hs-MoP/NPSC electrocatalyst exhibits an encouraging HER activity with a low overpotential of only 70 mV at a current density of 10 mA cm-2, a small Tafel slope and long-term durability in alkaline media, outperforming most of reported Pt-free MoP-based electrocatalysts to date. This present work not only develops a highly efficient electrocatalyst for HER, but also opens up opportunities to engineer novel architectures for various applications.