A shelf-stable and versatile heptafluoroisopropylthiolating reagent N-heptafluoroisopropylthiophthalimide (Phth-SCF(CF3)2) was developed. It is readily accessible from the reaction of di(1-phthalimidyl)disulfane with AgCF(CF3)2. The widely synthetic application of this reagent has been demonstrated by nucleophilic substitution of alkyl halides, deoxygenative heptafluoroisopropylthiolation of alcohols, electrophilic aromatic substitution of indoles, radical heptafluoroisopropylthiolation of alkenes, and cross-coupling with alkynes.