A method for generation of SVI sulfones from β-sulfinyl esters (SIV) under transition-metal-free non-oxidative mild conditions is presented. Various sulfones have been achieved with moderate to excellent yields. The advantage of using β-sulfinyl esters as masked aryl sulfinates has also been exemplified using brominated substrates. Oxygen isotope-labeling experiments indicated that the oxygen atoms incorporated into the sulfone product come from the sulfoxide of the β-sulfinyl ester. Successive β-elimination/O-addition/sulfinate esterification/β-elimination processes are proposed for the mechanism of generating SVI from SIV.