Sulfonyl fluorides are useful building blocks in a wide array of fields. Herein, we report a catalytic decarboxylative fluorosulfonylation approach for converting abundant aliphatic carboxylic acids to the corresponding sulfonyl fluorides. This transformation is enabled by simple preactivation as aldoxime esters and energy-transfer-mediated photocatalysis. This operationally simple method proceeds with high functional-group tolerance under mild and redox-neutral conditions.