In this report, we present a photocatalytic ring-opening fluorosulfonylation of strained cycloalkanols with sulfur dioxide and NFSI under mild conditions for the synthesis of carbonyl-containing aliphatic sulfonyl fluorides. The synthetic potential of the carbonyl-containing aliphatic sulfonyl fluoride products has been examined by diverse transformations, including SuFEx reactions and Baeyer-Villiger oxidation reactions. Mechanistic studies demonstrate that the reaction operates through a radical C-C bond cleavage/SO2 insertion/fluorination cascade process.