As energy storage materials, transition metal phosphides have attracted recent attention. In this paper, FeP hollow nanorods were fabricated with hydrothermally synthesized MoO3 nanofibers as a template. The chemical composition, morphological structure and synthetic process of such a product were characterized. Its supercapacitive properties as an electrode material were also investigated. The results show that the developed FeP hollow nanorods have a porous nature with the specific surface area (i.e., 277.4 m2/g) and well-defined interior of about 30 nm thick shell due to the stack, aggregation and adhesion of FeP nanoparticles. The FeP hollow nanorod electrode with a unique morphological structure and a large specific surface area has a superior supercapacitive behavior with the maximum specific capacitance of 243.6 F/g, remarkable rate capability as well as outstanding cycling stability. The capacitance decay of only 13.8% can be achieved after consecutive charge/discharge for 10 000 cycles at a large current density of 5 A/g. The electrochemical performance of FeP hollow nanorods is better than that of some Fe-based supercapacitor electrode materials previously reported.