The growing global demand for renewable energy sources has pushed renewable, green energy sources to the forefront, among which the production of hydrogen gas from water occupies a significant place. To realize this goal, researchers across the globe are developing various systems that could swiftly catalyse the hydrogen evolution reaction (HER) in the highest possible yield. In the present work, we report electrocatalytic HER performances of pyridoxal semicarbazone- and thiosemicarbazone-based Cu(II) complexes, i.e. ([Cu(PLSC)Cl2] and [Cu(PLTSC-H)H2O]Br?H2O). We unambiguously demonstrated that the complexes exhibit enviable level of HER catalytic activity. The catalytic activity of the complexes was not only the function of central metal but it was also controlled by the nature of the coordinating ligand.