Herein, we report the synthesis of uniform hollow nanorods of Ni-doped FeP nanocrystals hybridized with carbon as electrocataysts for the electrocatalytic hydrogen evolution reaction (HER). These hollow nanorods are prepared based on the etching and coordination reaction between metal-organic frameworks and phytic acid, followed by a pyrolysis process. Benefiting from the abundant active sites, the improved mass and charge transport capability, the optimized Ni-doped FeP/C hollow nanorods exhibit excellent HER activities for achieving a current density of 10 mA cm−2 at an overpotential of 72, 117, and 95 mV in acidic, neutral, and alkaline media, respectively, as well as superior stability. X-ray photoelectron spectroscopy and basic density functional theory calculations suggest that the improved HER activity originates from the synergistic modulation of the active components, structural and electronic properties. This protocol provides a general and friendly strategy to construct hollow phosphides for energy-related applications. Hydrogen generation through water splitting is considered as a green and efficient way to meet the increasing demands for renewable and clean energy s...