A gold-catalyzed oxidative three-component reaction of terminal alkynes with alcohols and quinone monoimines has been disclosed, affording α-ketoacetals in good to excellent yields. By using quinone monoimines as electrophiles for the interception of the in situ generated gold enolate intermediate, this one-pot process provides an unprecedented method for the polyfunctionalization of terminal alkynes through an oxidation-oxyalkylation-aryloxylation sequence, installing three oxygen atoms on the C-C triple bond.