Controllable chemoselectivity and regioselectivity synthesis of 3‐sulfinylated, 3‐sulfenylated and 2‐sulfonylated indoles via direct C−H functionalization are realized under metal‐free conditions. In particular, the synthesis of 3‐arylsulfinylindoles in high yields from a sulfone substrate in water without additives is reported. The process displays excellent functional groups compatibility. p‐Toluenesulfonyl cyanide (TsCN) possesses a hexavalent sulfonyl group, as an odorless and easy‐to‐handle solid, which has been used as a new sulfur reagent through the cleavage of S−C and S=O bonds in our work. [ABSTRACT FROM AUTHOR]