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Developing high-efficient and Earth-abundant electrocatalysts toward hydrogen evolution reaction (HER) is strongly desired for electrochemical water splitting but remains a considerable challenge. Herein, we propose a 3D hierarchical Fe(PO 3) 2 @Cu 3 P heterostructure nanotube arrays on Cu foams for promising HER catalysts. The HER performance can be tuned by changing FeCl 3 concentrations and the optimized cathode exhibits excellent HER activity in 1 M KOH with a low overpotentials of 108 mV @ 10 mA cm−2 and a small Tafel slope of 84 mV dec−1. Furthermore, this electrode delivers high electrochemical durability with stable operation for 24 h. Such high performance can be ascribed to the unique hierarchical heterostructure with large electrochemical surface area, synergistic effect and fast electron transport. Our study can provide new inspiration for rational construction of copper-based hierarchical nanomaterials for HER electrodes and other energy-related applications. Hierarchical Fe(PO 3) 2 @Cu 3 P nanotube hybrids on 3D copper foam were synthesized, which demonstrate excellent activity toward hydrogen evolution in alkaline solution with robust stability. Image 1 • Hierarchical Fe(PO 3) 2 @Cu 3 P nanotube arrays were successfully synthesized on Cu foam. • The hybrid catalysts exhibit excellent activities for HER in alkaline media. • Synergistic effect between Fe(PO 3) 2 and Cu 3 P was found by XPS. • The hybrid catalyst exhibits considerable stability for HER. [ABSTRACT FROM AUTHOR]