AbstractA three‐component thioamination reaction has been developed in the presence of phenyliodonium(III) diacetate (PIDA) leading to the formation of a thioaminated products. This catalytic approach represents a method for the metal‐free thioamination of 1,4‐naphthoquinone. It was observed that maleimides also work smoothly under this metal‐free reaction condition. This present method implies the oxidative coupling reaction through a one‐step process with the generation of C−N and C−S bonds. Various aromatic and aliphatic thiols and amines provided the corresponding thioaminated compounds in 62–88% yields. A plausible reaction pathway has been predicted according to few control experiments.magnified image