Ionic liquid/carbon nanotubes (IL/CNTs) composite was applied as the precursor to prepare CNTs-supported cobalt phosphide via low-temperature phosphidation. CoP(vmmG)/CNTs, generated from N,N-bis(4-(methoxycarbonyl)benzyl)-N-methyl-d-glucaminium dibromo-dichlorocobaltate(II) (MBMG)(2)-CoCl2Br2), exhibits the best catalytic activity toward hydrogen evolution reaction with an onset overpotential of 55 mV, a Tafel slope of 58 mV dec(-1), 95% Faradaic efficiency (FE), current densities of 10 and 20 mA cm(-2) at overpotentials of 135 and 160 mV, and it can maintain the catalytic activity for at least 27 h. FT-IR, Raman spectroscopy, XPS and XRD were utilized to investigate the phosphidation process. All experimental results confirmed that anion from (MBMG)(2)-CoCl2Br2 can form CoP and glucaminium-based cation can become amorphous carbon after phosphidation to obtain the high HER activity of CoPov/BmG/CNTs. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.