We prepared WCeO2 (M = Fe, Co or Ni) by coprecipitation method, and then fabricated M@CNT/CeO2 electrocatalysts through ethanol decomposition on WCeO2. Experimental results showed that the activity of Co@CNT/CeO2 for hydrogen evolution reaction (HER) was much higher than that of Fe@CNT/CeO2 and Ni@CNT/CeO2, these experimental results were consistent with the density functional theory (DFT) calculation results. The electrocatalysts from ethanol decomposition on Co/CeO2 at 800 degrees C with different time were obtained, and their electrocatalytic activities for HER were discussed. Co@CNT-90 showed higher activity than others, when the reaction time exceeded 90 min, their HER activities declined gradually, because long-term ethanol decomposition caused decreased dispersion and thicker layers of carbon nanotube (CNT). To obtain a current density of 10 mA cm(-2), overpotential of 181 mV was required for Co@CNT-90, and its polarization curve after 8000 cycles retained a similar performance to the initial polarization curve. The high activity and durability of Co@CNT-90 could be explained from the carbon-encapsulated-metal structure, thus metal was protected by carbon layers and prevented metal from contacting with electrolyte directly. XRD patterns, TEM images and experimental results proved that Co was well encapsulated by CNT. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.