We now report the electrocatalytic dehydrogenation of tetrahydroquinaldine by an electron-rich CpNi N-heterocyclic carbene (NHC) with quinoid ligand motifs and explore the effects of quinone additives on CpNi compounds without quinoid NHC ligands. Our CpNi(NHC) catalyst exhibits dehydrogenative electrocatalytic activity and demonstrates that a molecular catalyst precursor can be viable in the electrode-driven (H⁺ + e⁻) release step of “virtual hydrogen storage”.