Polyheteroaromatic compounds are potential optoelectronic conjugated materials due to their electro- and photochemical properties. Transition-metal-catalyzed multiple C鈥揌 activation and sequential oxidative annulation allows rapidly assembling of those compounds from readily available starting materials. A rhodium-catalyzed cascade oxidative annulation of 尾-enamino esters or 4-aminocoumarins with internal alkynes is described to access those compounds, featuring multiple C鈥揌/N鈥揌 bond cleavages and sequential C鈥揅/C鈥揘 bond formations in one pot.