Through β-activation of alkynoic acid esters with Nheterocyclic carbene catalysis, a formal [3+3] annulation of alkynyl acylazoliums with indolin-3-ones has been developed for the rapid construction of structurally interesting benzofuro[3,2-b]pyridin-2ones with potential bioactivities. This protocol provides a highly efficient and simple method for the synthesis of the target molecules under mild reaction conditions with a wide substrate scope and excellent chemoselectivity. The synthetic utility of this protocol was also demonstrated by the versatile late-stage modifications.