The 1,4-benzdiyne equvalent, [2,5-bis(trimethylsilyl)-4-(trifyloxy)phenyl](phenyl)iodonium triflate, was prepared from sodium 2,4,5-trichlorophenoxide. The chemoselective generation of an aryne from the side of the phenyliodonio group was observed after treatment with a fluoride ion. Double cycloaddition of 1,4-benzdiyne with different arynophiles was conducted in one pot, giving bis-cycloadducts in high yields. Similarly, the 1,3-benzdiyne equivalent bearing phenyliodonio and triflate groups was prepared from sodium 2,3,6-trichlorophenoxide. The 1,3-benzdiyne equivalent also underwent the chemoselective stepwise generation of arynes and the double cycloaddition with different arynophiles. These hybrid benzdiyne equivalents provided the double cycloadducts in high yields and enabled the convenient one-pot procedure for synthesis of polycyclic aromatic compounds.