Searching for low-cost electrocatalysts with high activity towards the hydrogen evolution reaction (HER) is of great significance to enable large-scale hydrogen production via water electrolysis. In this study, by using inverse spinel MFe2O4 (M = Mn, Fe, Co, Cu) nanoparticles (NPs) as the precursors, monodisperse bimetallic phosphide M-Fe-P NPs/C with hollow structures were readily obtained by a gas-solid annealing method. These hollow phosphide NPs displayed excellent HER activity in an acidic medium with a low loading amount of 0.2 mg cm(-2). In particular, the Co-Fe-P NPs/C shows highest HER activity that only requiring an overpotential of 97 mV to retain a current density of 10 mA cm(-2). A volcano relation between activity and incorporated elements was revealed. Incorporation of cation with high electronegativity stabilized the FeP active centres, while phase segregation resulted in the loss of activity for Cu-Fe-P NPs/C. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.