A direct and efficient approach to access structurally interesting 2,3-diperfluoroalkylated quinoxalines via selenium-catalyzed reductive C-C construction of vicinal bis(perfluoroalkyl formimidoyl chloride)s has been disclosed. This protocol features the use of easily accessible starting materials, scalability, and a diverse functional group tolerance. Mechanism studies suggested that this reaction may involve an interesting selenium-containing seven-membered-ring intermediate and proceed through an electrocyclization/selenium reductive elimination pathway, which is significantly different from the traditional transition-metal-catalyzed reductive coupling strategies of alkyl halides.