A direct and facile palladium-catalyzedC–H bond oxidative carbonylation reaction and oxidative cyclization for the synthesis of polycyclic aromatic hydrocarbons (PAHs) is reported herein. The intramolecular cyclocarbonylation, throughC–Hactivation and C–C, C–O bond formations under mild conditions, proceeds smoothly with good functional group tolerance in high to excellent yields. The intramolecular