An efficient method for generating 3-triazenylarynes from ortho-iodoaryl triflate-type precursors was developed. The generated arynes reacted with various arynophiles with high regioselectivity because of the triazenyl group. The 3-triazenylaryne precursors functioned as useful intermediates of diverse multisubstituted aromatic compounds through the transformation of the remaining triazenyl group of aryne adducts and triazenyl group-directed ortho-C-H functionalization.