A stereoselective N-alkenylation of azoles with alkynes and iodine(III) electrophile is reported. The reaction between various azoles and internal alkynes is mediated by benziodoxole triflate as the electrophile in a trans-fashion, affording azole-bearing vinylbenzio- doxoles in moderate to good yields. The tolerable azole nuclei include pyrazole, indazole, 1,2,3-triazole, benzotriazole, and tetra- zole. The iodanyl group in the product can be leveraged as a versatile synthetic handle, allowing for the preparation of hitherto inac- cessible types of densely functionalized N-vinylazoles.