An efficient, green strategy has been developed to synthesize β‐keto sulfones using available and inexpensive sulfonyl chlorides as a sulfur source in reaction with aromatic alkenes in the presence of cheap iodide. It is particularly pointed out that this method involves the construction of C−S bonds and the desired product can be obtained either through the free radical pathway. This agreement involves a green and simple synthesis method, and is functionalized with styrene and the present method is applicable to a wide range of benzenesulfonyl chloride compounds and styrenes with a variety of functional groups. [ABSTRACT FROM AUTHOR]