An expert and easy one-step catalytic method for the multi O-C coupling of alkyne is developed for the synthesis of valuable α-ketoesters and their chiral analogues, in contrast to the generation of esters by a noncatalytic method. The in situ generated powerful Ag(II) catalyst from AgOTf is the workhorse in the oxidative grafting of alkyne with PhIO and alcohol. The radical mechanism is confirmed in our controlled experiments and UV-vis study.