An efficient, clean and versatile strategy for the synthesis of 2,3,4‐triiodoanisole via one‐pot microwave‐assisted/Pd‐catalyzed domino C‐H iodination/ipso‐iododecarboxylation of 3‐anisic acid is presented. Significantly, the product is crystalline and bench stable solid which can be performed in good isolated yield. This report described a protocol for the first synthesis of hitherto unknown 2,3,4‐triiodoanisole that is catalytic, clean and scalable. Remarkably, the Suzuki‐Miyaura cross‐coupling reactions on the later compound were also demonstrated as a precursor providing 2,3‐diiodo‐4‐methoxybiphenyl and iodinated terphenyl derivatives in good yields and in excellent site‐selectivity.