AbstractThe cationic polymerization of isobutene vinyl ether(IBVE) contains waters system was achieved by using triphenylmethylium tetrakis‐(pentafluorophenyl)borate [Ph3C][B(C6F5)4], which overcame the harsh experimental requirements of traditional cationic polymerization. The influences of water content, solvent polarity, and reaction temperature on polymerization were studied. The end structure of the polymer was analyzed by 1H‐NMR. Combined with the effect of the proton trapping agent and triethylamine salt which can trap [H+], it was found that there was a reversible equilibrium between [Ph3C+] and [H+] active species during the polymerization process. The cationic polymerizations of isobutyl vinyl ether were initiated by these two active species simultaneously. The controllable cationic polymerization of isobutyl vinyl ether was achieved by the addition of ethyl methyl carbonate and ethyl benzoate. Gaussian 09 W simulation confirms the polymerization mechanism.