A variety of α-arylated sulfoxonium ylides could be facilely synthesized in modest to high yields through α-arylation of sulfoxonium ylides with aryl fluorosulfates via C-O bond functionalization under palladium catalysis. Reactions using readily available and bench-stable aryl fluorosulfates as effective and appealing arylating agents showed both good substrate scope and broad functionality tolerance. Important functional groups such as nitro, cyano, formyl, acetyl, methoxycarbonyl, trifluoromethoxy, fluoro, and chloro embedded in substrates remained intact during the course of the reaction, and could be subjected to downstream modification. In addition, the reaction could be readily scalable and applied in the late-stage modification of complex molecules.