A green and economical electrochemical protocol has been developed to synthesize polycyclic (hetero)aromatic compounds by the [4+2] benzannulation of biaryldiazonium salts with alkynes. This protocol features a broad substrate scope. Instead of requiring diazonium reagents, these reactions can begin from anilines and can be carried out in one pot. Moreover, the readily accessible scale-up synthesis achieved by using an electrochemical flow cell demonstrates the synthetic potential of this protocol.