Creation of robust and stable electrocatalysts is a persistent objective for high-efficiency hydrogen evolution by water splitting. We present here the experimental realization of one-dimensional Mo incorporated W18O49 nanofibers (NFs) by a template-free solvothermal method. When utilized as electrocatalysts for hydrogen evolution through water splitting, the preliminary results demonstrate that the optimized catalytic electrode from 1 at% Mo doped W18O49 NFs yields an onset overpotential of 89 mV and Tafel slope of 49 mV dec(-1) as well as maximal exchange current density up to 1.60 x 10(-2) mA cm(-2).An overpotential as low as 462 my is required to attain current density of 50 mA cm(-2) in comparison with 587 mV for pristine W18O49 NFs. Moreover, the Mo doped W18O49 NFs display relative stability by applying a potential of 503 mV and a current density of 80 mA cm(-2) over 24 h in 0.5 M H2SO4 aqueous solution, making them promising in practical applications. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.