In the past decade, the use of redox-active ligands has emerged as a promising strategy to improve catalyst selectivity, efficiency, and stability in electroassisted H+ and CO2 reductions. Partial delocalization of the electrons within ligand-centered orbitals has been proposed to serve as an electron reservoir, as a catalytic trigger, or as a way to prevent deleterious low-valent metal center formation. However, conclusive evidence of these effects is still scarce, and open questions remain regarding the way redox-active ligands may affect the catalytic mechanism. In this Perspective, advances in redox-active ligands in electroassisted catalytic H+ and CO2 reductions are discussed through recent representative examples.