Developing a green and efficient method for synthesizing vinyl sulfones is challenging and highly desirable. We herein report a green, sustainable, and unprecedented mechanochemical-assisted approach for the decarboxylative sulfonylation of α,β-unsaturated carboxylic acids with sodium sulfinates using only potassium iodide (50 mol%) as an activator under water-assisted grinding conditions. A library of alkyl and aryl vinyl sulfone derivatives were synthesized successfully in up to 92% yield with excellent functional group compatibility in a short reaction time. This sulfonylation strategy is well tolerated by aryl α,β-unsaturated carboxylic acids and alkyl and aryl sodium sulfinate salts. The method has been successfully applied to the synthesis of neuroprotective agents. Overall, the advantages of this strategy are (i) metal catalyst-, base-, oxidant-, and solvent-free conditions, (ii) operational simplicity with a short reaction time, and (iii) excellent effective mass yield, atom economy, E-factor, and EcoScale score. The practicality of this method is also demonstrated in the gram-scale synthesis of vinyl sulfones.