γ-Keto sulfones are versatile building blocks and valuable intermediates in organic synthesis and pharmaceutical chemistry. Motivated by their excellent properties, we herein report a green, convenient, metal-free hydrosulfonylation method for a variety of ynones, vinyl ketones, and sodium sulfinates in the absence of stoichiometric oxidants. This operationally simple protocol provides straightforward and practical access to a wide range of γ-keto sulfones with broad functional group tolerance from easily available starting materials. Moreover, the β,γ-unsaturated keto sulfones could further react with 2,3-butadienoate to generate cyclopentenes in phosphine-mediated [3 + 2] cycloaddition.