Monodentate chelation-assisted direct ortho-C-H sulfonylation of (hetero)arenes using TosMIC as the novel sulfonylating reagent has been developed. A broad range of substrates, including indolines, indoles, 2-phenylpyridines, and others were well tolerated to afford the corresponding products in moderate to good yields. Mechanistic studies revealed that the sulfonyl radical might be involved. Inspired by the above discovery, preliminary para-C-H sulfonylation of naphthalene substrate was also successfully realized. The current protocol featured with cheap metal catalysis, good functional group compatibility, and operational convenience.