A new efficient method for the preparation of α-keto esters via a free radical acylation approach using phenylsulfonyl methoxycarbonyl oxime ether 1 has been developed. When an alkyl iodide was treated with 1, hexamethylditin, and acetone in THF at 300 nm for 3 h, α-keto ester 3 was obtained in high yield after hydrolysis of the oxime ether 2.