Abstract The title transformation can be achieved by the o-C–H cleavage of alkynyl aryl ethers, which is easily derived from phenols, followed by the insertion/annulation with isocyanates in the presence of a palladium catalyst. Various alkynyl aryl ethers and arylisocyanates are applied to this transformation to give the corresponding cyclic products. Mechanistic study indicates that the C–H cleavage is effected reversibly by the concerted metalation-deprotonation pathway. The products exhibit solid-state luminescence upon irradiation of UV light. Fluorescent maxima and quantum yields can be controlled by the substituents at appropriate sites in the products.