Nowadays, hydrogen has become not only an extremely important chemical product but also a promising clean energy carrier for replacing fossil fuels. Production of molecular H2 through electrochemical hydrogen evolution reactions is crucial for the development of clean-energy technologies. The development of economically viable and efficient H2 production/oxidation catalysts is a key step in the creation of H2-based renewable energy infrastructure. Intrinsic limitations of both natural enzymes and synthetic materials have led researchers to explore enzyme-induced catalysts to realize a high current density at a low overpotential. In recent times, highly active widespread numerous electrocatalysts, both homogeneous or heterogeneous (immobilized on the electrode), such as transition metal complexes, heteroatom- or metal-doped nanocarbons, metal-organic frameworks, and other metal derivatives (calix  resorcinols, pectates, etc.), which are, to one extent or another, structural or functional analogs of hydrogenases, have been extensively studied as alternatives for Pt-based catalysts, demonstrating prospects for the development of a “hydrogen economy”. This mini-review generalizes some achievements in the field of development of new electrocatalysts for H2 production/oxidation and their application for fuel cells, mainly focuses on the consideration of the catalytic activity of M[P2N2]2 2+ (M = Ni, Fe) complexes and other nickel structures which have been recently obtained.