We describe in this paper an original synthetic route to alternating pi-conjugated copolymers, based on the electrochemical preparation of intermediate aryldizinc species and their subsequent coupling with unsaturated dihalogenated compounds. This method was first applied to the preparation of poly(p-phenylenevinylenes) (PPVs). The structural and redox properties of PPVs prepared in this way are discussed. Some copolymers exhibiting alternating phenyl and thienyl units are also prepared according to this procedure.