Gold-catalyzed oxidations of thioalkynes with 8-methylquinoline oxides afford 2-phenylthioketenes that can be trapped efficiently with alcohols. The synthetic utility is manifested by terminal and internal thioalkynes over a wide scope, bearing esters, ketones, alkyl, and oxime substituents. Our density functional theory calculations suggest that gold-catalyzed oxidations of terminal and internal thioalkynes with 8-methylquinoline oxides generate gold-bound ketene intermediates without the intermediacy of α-oxo gold carbene.