A domino-type multiple C-H functionalization of tetracene with molecular benzene is reported. Under the typical conditions of the Scholl reaction, a domino reaction occurs between tetracene and six molecules of benzene in one pot to furnish an aromatic compound with a curved π-system. This reaction sequence involves oxidative cross-dehydrogenative coupling/annulation and Friedel-Crafts-type reactions. Eight C-C bonds are formed via this intermolecular domino reaction without mediation by a metal or the assistance of a specific substituent.