An electrochemical dehydrogenative homo-coupling reaction of imidazopyridine-based heterocycles has been developed, which affords biheteroaryls with good chemical yields and high regioselectivities. This reaction is conducted in a simple undivided cell at room temperature, which avoids the use of any metal-catalysts, additives and oxidants. This reaction tolerates a wide scope of substrates, which provides an easy and green strategy for the preparation of important bioactive biheteroaryl compounds.