Electrochemistry has been an increasingly useful tool for organic synthesis, as it can selectively generate reactive intermediates under mild conditions using an applied potential. Concurrently, synergistic activity of a metal and a ligand has been used in thermal catalysis and electrocatalytic renewable fuel generation for substrate selectivity and improved catalyst activity. Combining these synthetic strategies is an attractive approach for mild, selective, and sustainable electrosynthesis. This perspective discusses examples of metal-ligand synergistic catalysis in electrochemical applications in organic and organometallic synthesis. The range of reactions and ligand design principles illustrates many opportunities for further discovery in this area and the potential for far-reaching synthetic benefits.