Water splitting is a promising approach for storing intermittent renewable energies, such as sunlight in the clean chemical bonds as a hydrogen fuel. Two water-soluble octahedral cobalt (III) complexes, [Co(bpb)(OAc)(H2O)], 1, (bpb(2-) = N,N' -bis[(2-pyridine carboxamide)-1,2-benzene] dianion) and [Co(cbpb)(OAc)(H2O)], 2, (cbpb(2-) = N,N'-bis[(2-pyridine carboxamide)-4-chloro-1,2-benzene] dianion) were synthesised and characterised by CHN elemental analysis, UV-Vis, FT-IR and single-crystal X-ray diffraction techniques. The two carboxamide ligands had been prepared in the ionic liquid TBAB as an environmentally benign reaction medium. The electrocatalytic water splitting activity of 1 and 2 showed that both complexes are highly active for the water splitting in aqueous solutions. Turn Over Frequency (TOF) values were, for 1 and 2 respectively, 527 and 490 mol of hydrogen in each mole of catalyst per hour at an overpotential of 738 mV (pH = 7.0). Such a performance can be ascribed to the flat ligands, the electroactivity of the metal centre and carboxamide ligands and the ability of losing the axial ligands around the metal-ion centre during the reduction process which provide different reduction pathways for an HER process. (C) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.