A nickel based molecular catalyst [Ni(QCl-tpy) 2 ]Cl 2 ·7H 2 O (where QCl-tpy = 2-choloro-3-(2,6-di (pyridin-2yl)pyridine-4-yl) quinoline) has been synthesized, characterized by single crystal XRD and other spectroscopic techniques. The complex [NiII(QCl-tpy) 2 ]2+ has also been employed for the electrocatalytic proton reduction in DMF/H 2 O (95:5 v/v) using trifluoro acetic acid (TFA) as the proton source. It exhibits a reasonably efficient catalytic ability towards proton reduction under organic media. Compared to the parent [NiII(tpy) 2 ]2+ during the electro-catalysis, the complex [NiII(QCl-tpy) 2 ]2+ behaves as a better catalyst in terms of higher catalytic current and 180 mV of lower overpotential as well. It is expected due to the presence of 2-chloroqinoline moiety in the terpyridine framework. The rate of H 2 evolution was analysed with the use of Foot-of-the Wave Analysis (FOWA) method. The complex shows a TOF of 3.68 s−1 as obtained from Foot-of-the Wave Analysis (FOWA) at the scan rate 100 mVs−1 for 1.0 mM [NiII(QCl-tpy) 2 ]2+ complex. The acid base equilibria reveals the dechelation followed by protonation at one of the coordinated pyridine rings of the QCl-tpy ligand. There could be a pendant base effect towards hydrogen evolution due to dechelated pyridine ring of the coordinated QCl-tpy ligand, which acts as a proton relay. Based on the spectroscopic evidence and electrochemical studies a plausible mechanism for the reduction of proton to H 2 has been proposed. Image 1 • Complex [Ni(QCl-tpy) 2 ]Cl 2 ·7H 2 O has been synthesized and characterized by single-crystal XRD. • The complex is capable of generating hydrogen from trifluoroacetic acid (TFA). • The kinetics of H 2 evolution was analysed by Foot-of-the Wave Analysis (FOWA) method. • The complex shows a TOF of 3.68 s−1 as obtained from FOWA. • Pendant base effect towards hydrogen evolution due to dechelation of the ligand is the key factor. [ABSTRACT FROM AUTHOR]