In order to solve the problems of fossil energy depletion and environmental pollution, it is necessary to find new energy sources that are recyclable and environmentally friendly. Among them, hydrogen is a high calorific value, clean and sustainable energy. At present, hydrogen is mainly obtained by electrolysis of water. The use of electrocatalysts in this process can effectively reduce the consumption of elec. energy. In this study, three mol. electrocatalysts based on nickel complexes, [BzTPP]2[Ni(mnt)2](1), [BzTPP]2[Ni(i-mnt)2](2), and [BzTPP]2[Ni(tdas)2](3) ([BzTPP]+ = 1-benzyltriphenylphosphinium, mnt = 1,2-dicyanoethylene-1,2-dithiolate, i-mnt = 1,1-dicyanoethylene-2,2-dithiolate and, and tdas = 1,2,5-thiadiazole-3,4-dithiolate), were systemically investigated. Electrochem. study showed three complexes can electrocatalyze hydrogen generation from acetic acid or aqueous buffer solution, and afford a turnover frequency (TOF) of 504.76, 591.52 and 1022.93 mol of hydrogen per mol of catalyst per h at an overpotential (OP) of 0.838 V from a neutral buffer. It is shown that [NiII(tdas)2]2-exhibits higher electro-catalytic hydrogen production activity than [NiII(mnt)2]2- and [NiII(i-mnt)2]2-. This provides a new chem. paradigm for the design and fabrication of efficient mol. catalysts for water reduction