Ionic liquids have been employed to pretreat coal to modify its network structure, and thus to improve the electroreduction activity of coal on a Ni-W-B catalytic electrode. Among the pretreatment solvents, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) exhibits the best performance of coal extraction and swelling. The coal sample is pretreated by [Bmim]Cl at optimized temperature (150 degrees C), then the pretreated coal is analyzed and characterized by scanning electron microscopy, gas chromatograph, infrared spectroscopy and linear sweep voltammetry. The results show that the coal network is fractured, resulting in a loose and porous structure, which facilitates hydrogenation reactions of coal on the catalytic electrode. A liquefaction yield of 57.6% is realized after electrolysis of coal on the catalytic electrode for 24 h at -1.7 V in a NaOH + H2O + tetrabutylammonium bromide mixed electrolyte system, 15% higher compared to the coal without pretreatment (40.3%). The mechanism for the pretreatment of coal in ionic liquids has been proposed. (C) 2015 Elsevier Ltd. All rights reserved.