The hypervalent iodine mediated, silica gel promoted synthesis of 2‐aminobenzazoles and 2‐aminobenzothiazole derivatives under metal‐free mild conditions within short time (30min) has been developed. Under this process, PhI(COOCF3)2 (PIFA) or PhI(COOCH3)2 (PIDA) acts as an oxidant and radical initiator direct activated the ortho‐C‐H bond of substrate, silica gel as weakly lewis acid effectively increased the reactivity of the reaction system. This method is compatible with various of arylurea and arylthiourea substrates, which is green, efficient, simple to operate and suitable for practical application.