The ¹⁸F labeling of unprotected peptides and sugars with a Au(III)-[¹⁸F]fluoroaryl complex is reported. The chemoselective method generates ¹⁸F-labeled S-aryl bioconjugates in an aqueous environment in 15 min with high radiochemical yields and displays excellent functional group tolerance. This approach utilizes an air and moisture stable, robust organometallic Au(III) complex and highlights the versatility of designer organometallic reagents as efficient agents for rapid radiolabeling.