Three transition metal complexes (MC) namely, [Tp(MeMe)CuCl(H2O)] (CuC), [Tp(MeMe)NiCl] (NiC), and [Tp(MeMe)FeCl(2)(H2O)] (FeC) {Tp(MeMe) = tris(3,5-dimethylpyrazolypborate) were synthesized and structurally characterized. The three complexes CuC, NiC, and FeC-modified glassy carbon (GC) were examined as molecular electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution (0.1 M KOH). Various GC-MC electrodes were prepared by loading different amounts (ca. 0.2-0.8 mg cm(-2)) of each metal complex on GC electrodes. These electrodes were used as cathodes in aqueous alkaline solutions (0.1 M KOH) to efficiently generate H-2 employing various electrochemical techniques. The three metal complexes' HER catalytic activity was assessed using cathodic polarization studies. The charge-transfer kinetics of the HER at the (GC-MC)/OH- interface at a given overpotential were also studied using the electrochemical impedance spectroscopy (EIS) technique. The electrocatalyst's stability and long-term durability tests were performed employing cyclic voltammetry (repetitive cycling up to 5000 cycles) and 48 h of chronoamperometry measurements. The catalytic evolution of hydrogen on the three studied MC surfaces was further assessed using density functionaL theory (DFT) simulations. The GC-CuC catalysts revealed the highest HER electrocatalytic activity, which increased with the catalyst loading density. With a low HER onset potential (E-HER) of -25 mV vs. RHE and a high exchange current density of 0.7 mA cm(-2), the best performing electrocatalyst, GC-CuC (0.8 mg cm(-2)), showed significant HER catalytic performance. Furthermore, the best performing electrocatalyst required an overpotential vaLue of 120 mV to generate a current density of 10 mA cm(-2) and featured a Tafel slope value of -112 mV dec(-1). These HER electrochemical kinetic parameters were comparable to those measured here for the commercial Pt/C under the same operating conditions (-10 mV vs. RHE, 0.88 mA cm(-2), 108 mV dec(-1), and 110 mV to yield a current density of 10 mA cm(-2)), as well as the most active molecular electrocatalysts for H-2 generation from aqueous alkaline electrolytes. Density functional theory (DFT) simulations were used to investigate the nature of metal complex activities in relation to hydrogen adsorption. The molecular electrostatic surface potential (MESP) of the metal complexes was determined to assess the putative binding sites of the H atoms to the metal complex.