Two bis(benz)imidazolium salts alkylated with pyridyl side arms, H2L1Br2 (1,2‐bis{[1‐(2‐pyridylmethyl)benzimidazolium‐3‐yl]methyl}benzene bromide) and H2L2Br2 (1,2‐bis{[1‐(2‐pyridylmethyl)imidazolium‐3‐yl]methyl}benzene bromide) have been prepared and were used as precursors in the synthesis of novel nickel compounds of N‐heterocyclic carbenes (Ni‐NHCs). The four Ni‐NHC complexes [Ni(L1)Br]Br (1a), [Ni(L1)](PF6)2 (1b), [Ni(L2)]Br2 (2a) and [Ni(L2)](PF6)2 (2b) were isolated and characterized by various methods, and the X‐ray crystal structures of 1a, 2a and 2b are reported. The nickel ion in 1a is in a square‐pyramidal geometry with one of the bromide ions in the apical position, the nickel ions in 2a and 2b are in square‐planar geometries. The compounds of the ligand with an imidazole‐based carbene revealed much higher activity in electrocatalytic proton reduction and better acid tolerance, although their overpotentials are higher than those of the benzimidazole‐based compounds. The presence of bromide ions has an adverse effect on the redox potentials as well as the overpotentials for proton reduction. Complex 2b, having the most planar coordination geometry, appeared to have the highest catalytic efficiency for proton reduction in DMF (ic/ip = 50, kobs = 490 s–1 at 0.1 V/s) when using acetic acid as the proton source. To the best of our knowledge, this is the first report of Ni‐NHC complexes that are active in electrocatalytic proton reduction.