Vitreous carbon (VC), pyrolytic carbon (PC) and moulded graphite (MG) were tested as cathodic materials in hydrogen production by water electrolysis in the presence of the ionic liquid tetrafluoroborate of 3-triethylammonium-propane sulfonic acid (TEA-PS.BF4). The physical characterization of the carbon materials indicated large differences in the microstructure of VC, PC, and MG and this significantly affected their electrochemical response. The mechanism presented for all the materials studied in the hydrogen evolution reaction (HER) was Volmer-Heyrovsky, where the H-2 desorption at the catalytic surface is the determining step. The MG electrode presented an unfavourable performance due to the formation of nanobubbles that coalesced without H-2 desorption and led to the deactivation of the catalytic sites. This behaviour is attributed to the presence of large and ordered crystallites at the material surface, with a greater number of hydrophobic domains in comparison with VC and PC material surfaces. The VC and PC electrodes presented a higher performance compared to the Pt cathode, showing lower activation energy, higher cathodic exchange current and lower charge transfer resistance. The set of results indicates VC and PC as promising alternative materials to constitute cathodes for the electrolysis of water using TEA-PS.BF4 aqueous solution as electrolyte. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.