The design of electrocatalysts for the oxidation and production of H 2 is important for the development of alternative energy sources. This Article focuses on the [Ni(P2RN2R′) 2]2+ electrocatalysts, where P2RN 2R′ denotes 1,5-diaza-3,7-diphosphacyclooctane ligands with substituent groups R and R′ covalently bound to the phosphorus and nitrogen atoms, respectively. Theoretical methods are used to investigate the mechanism of the step in the catalytic cycle corresponding to [HNi II(P2N2)2]+ - e - → [NiI(P2HN2)(P 2N2)]2+ for H2 oxidation and the reverse reaction for H2 production. This step involves electron transfer (ET) between the Ni complex and the electrode as well as proton transfer (PT) between the Ni and the N. The sequential mechanisms, PT-ET and ET-PT, are investigated for the following (R,R′) substituents: (Me,Me), (Ph,Ph), and (Ph,Bz), where Me, Ph, and Bz denote methyl, phenyl, and benzyl substituents. Density functional theory is used to calculate reduction potentials, pKa values, and PT pathways, and the inner- and outer-sphere reorganization energies for electrochemical ET are calculated within the framework of Marcus theory. For the (Ph,Ph) and (Ph,Bz) systems, the sequential PT-ET mechanism for H2 production would require surmounting a large free energy barrier for the initial PT step, followed by thermodynamically favorable ET. The sequential ET-PT mechanism for these systems would require a moderate initial applied overpotential, followed by a PT reaction with a relatively low free energy barrier. Consistent with experimental data, the calculated overpotential required for the initial reduction in the ET-PT mechanism is lower for the (Ph,Bz) system than for the (Ph,Ph) system for H2 production. The concerted mechanism, in which the electron and proton transfer simultaneously without a stable intermediate, may be thermodynamically favorable and is a direction of future research.