A series of new hypervalent iodine reagents based on the 1,3‐dihydro‐3,3‐dimethyl‐1,2‐benziodoxole and 1,2‐benziodoxol‐3‐(1H)‐one scaffolds, which contain a functionalized tetrafluoroethyl group, have been prepared, characterized, and used in synthetic applications. Their corresponding electrophilic fluoroalkylation reactions with various sulfur, oxygen, phosphorus, and carbon‐centered nucleophiles afford products that feature a tetrafluoroethylene unit, which connects two functional moieties. A related λ3‐iodane that contains a fluorophore was shown to react with a cysteine derivative under mild conditions to give a thiol‐tagged product that is stable in the presence of excess thiol. Therefore, these new reagents show a significant potential for applications in chemical biology as tools for fast, irreversible, and selective thiol bioconjugation. Fluoroalkylating agents: A series of new hypervalent iodine reagents that contain a functionalized tetrafluoroethyl group are prepared and used for electrophilic fluoroalkylations with S, O, P, and C nucleophiles (see scheme).