The direct acyloxyation of 2-(alkylthio)benzamide has been established via the amide-assisted α-C(sp³)–H functionalization in the presence of Selectfluor by employing simple carboxylic acid and its corresponding salt as acyloxy sources. This novel and simple method is characterized by its broad substrate scope in moderate to good yields and excellent functional group compatibility. Furthermore, this method also provides a complementary strategy to access important α-acyloxy sulfides and their derivatives.