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Generation of vinyl cations is facile by fragmentation of alkenyl(aryl)iodonium trifluoromethanesulfonates. Kinetics and electronic effects were probed by 1H NMR spectroscopy in CDCl3. Products of fragmentation include six enol triflate isomers in addition to iodoarenes. The enol triflates arise from direct reaction of a triflate anion with the starting iodonium salts as well as triflate reaction with rearranged secondary cations derived from those salts. G2 calculations of the theoretical isodesmic hydride-transfer reaction between secondary vinyl cation 7 and primary vinyl cation 6 reveal that cation 6 is 17.8 kcal/mol higher in energy. Activation parameters for fragmentation of (Z)-2-ethyl-1-hexenyl(3,5-bis-trifluoromethylphenyl)iodonium triflate, 17e, were calculated using the Arrhenius equation: Ea = 26.8 kcal/mol, ΔH⧧ = 26.2 kcal/mol, and ΔS⧧ = 11.9 cal/mol·K. Added triflate increases the rate of fragmentation slightly, and it is likely that for most β,β-dialkyl- substituted vinylic iodonium trifla...