Exploration of high-efficiency and inexpensive Pt-free electrochemical catalysts for hydrogen evolution reaction (HER) is highly significative for carbon dioxide free energy conversion systems. In this work, we described the development of CoSe2 nanoparticles grown on the carbon nanofibers (CNFs) derived from bacterial cellulose (CNFs/CoSe2) through a facile one-step hydrothermal preparation, which not only showed a three-dimensional (3D) porous network structure, but also possessed large surface area. This rationally designed architecture realizes the uniform distribution of CoSe2 nanoparticles to provide with fully exposed active edges and the unique conductive interwoven carbon nanofibers facilitates the charge transportation in HER process, thus leading to remarkable HER activity. As expected, the CNFs/CoSe2 shows a low onset overpotential of -85 mV, low overpotential (eta(10) = 119 mV) for reaching a current density of -10 mA cm(-2) and smaller Tafel slope of 54 mV dec(-1) as well as good cycling stability in acidic electrolyte. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.