Developing noble metal-free hydrogen evolution catalysts with excellent performance is of great significance but still remains a considerable challenge for electrocatalytic water splitting. This paper reports the synthesis of three-dimensionally ordered macroporous iron phosphide self-supported structure on carbon cloth (3DOM-FeP/CC) through an electrostatic self-assembly method along with heat-treatment and phosphidation. The resultant 3DOM-FeP/CC catalyst combined the advantages of the interconnected ordered macropores, the self-supported structure and the highly-conductive carbon substrate, which endowed the catalyst with substantial accessible active sites, abundant mass transport channels for electrolyte/products, and convenient electron transfer pathways. As a result, the 3DOM-FeP/CC catalyst exhibited outstanding catalytic activity for the hydrogen evolution reaction in acid electrolyte, providing a current density of 10 mA cm(-2) at an overpotential of 68 mV with a small Tafel slope of 42 mV dec(-1). This research provides a unique strategy to fabricate low-cost and high-efficiency catalysts for generating hydrogen from water. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.