Layered nanoporous Ti/TiO2/Ni-W-B electrode is prepared through electrochemical anodization and electrodeposition for electrocatalytic reduction of coal. Extensive characterizations of the layered nanoporous Ti/TiO2/Ni-W-B electrode have been performed using techniques including scanning electronic microscopy, X-ray diffraction, inductively coupled plasma, Brunauer-Emmett-Teller and linear sweep voltammetry. The results indicate that the electrode, which presents layered nanoporous surface network, exhibits high activity for the reduction of coal. In an organic electrolyte system, a liquefaction yield of 51.8% is obtained after electrolysis of coal on the prepared electrode for 24 h at -1.7 V. The electroreduction mechanism of coal is also investigated. IR and H-1 nuclear magnetic resonance results show that active hydrogen (H*) reacts with functional groups in the coal such as C=O, -C-O- and C=C, leading to the reduction of unsaturated bonds and the breakage of bridge bonds and part of aromatic rings during the electroreduction of coal. (C) 2014 Elsevier Ltd. All rights reserved.