General methods have not been previously developed for the synthesis of sterically hindered α-SCF3-substituted carbonyl compounds using nucleophilic trifluoromethylthiolating reagents. Thus, we herein report sp3C-SCF3 bond formation in hindered α-bromoamides containing 3-bromo-oxindoles and linear α-bromoamides using CuSCF3 or AgSCF3 under mild conditions to access sterically hindered α-SCF3-substituted amides. This transformation is applicable to not only 3-SCF3-substituted oxindoles but also primary and secondary amides and reveals a broad functional group tolerance. This method will benefit the fields of medicinal and agricultural chemistry.