C–H activation can offer an efficient synthetic route to access graphene segments or polycyclic aromatic hydrocarbons. In this work, we present the site-selective synthesis of triphenylene frameworks from unactivated arenes via 2- or 4-fold C–H arylation. A palladium-catalyzed annulative π-extension method leads to the straightforward synthesis of N-substituted triphenylenes with the employment of cyclic hypervalent iodine reagents. In addition, triphenylene-graphene hybrid architecture has been applied to a field-effect transistor to sense chemical vapors. This study may link graphene science and synthetic chemistry by providing a concise bottom-up synthetic route of graphene segments.