A Pd-catalyzed alkyne and aryne annulation strategy via C-H activation has been implemented for the synthesis of π-extended coumarins. This synthetic strategy provides a wide range of π-extended coumarins in moderate to good yields with good functional group compatibility. Photophysical properties of the synthesized π-extended coumarins have been evaluated, and some of them show interesting fluorescent properties. Three of the synthesized coumarins have been unambiguously established by a single-crystal XRD study.