An electrochemical intermolecular dehydrogenative coupling reaction of isothiocyanates with 2‐aminopyridines/amidines was developed. Using n‐Bu4NI as the catalyst and electrolyte, 1,2,4‐thiadiazoles and pyrido‐fused 1,2,4‐thiadiazoles were readily accessed with good to excellent efficiency under the undivided electrolysis conditions. This electrochemical approach obviates the use of external oxidants and transition‐metal catalysts.