Against the backdrop of the well-known O-sulfonylation of cyclopropyl alcohols with sulfonyl chlorides, we examined the feasibility of conducting regioselective C-sulfonylation. By emulating an umpolung strategy-guided design, we report for the first time the Cu(II)-catalyzed β-sulfonylation of cyclopropanols by a mechanism that potentially involves an oxidative addition of a sulfonyl radical to a metal homoenolate. Unlike reported methods, this protocol allows a practical synthetic route to γ-keto sulfone building blocks from cyclopropanols by leveraging commercially available aryl- and alkyl-sulfonyl chlorides, common reagents in organic chemistry laboratories. Using operationally simple open-flask conditions, the preparative scope of starting materials was demonstrated using an array of aryl- and alkyl-substituted sulfonyl chlorides and cyclopropanols (43 examples, up to 96% yield).