In this manuscript, the synthesis of an original SCF2PO(OEt)2‐containing reagent was depicted. Thanks to the unique properties of this newly‐designed source, an unprecedented transformation with aldehydes was conducted under radical conditions, offering an access to value‐added fluoroalkylthio compounds. Preliminary mechanistic studies were conducted and supported a radical reaction mechanism. Remarkably, thiol and disulfide derivatives turned out to be suitable coupling partners in a transition metal free transformation towards the synthesis of difficult‐to‐synthesize unsymmetrical disulfides. Finally, the difunctionalization of 4‐phenyl‐butene was investigated using this reagent.

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