A highly effective initiating system has been achieved for living cationic polymerization of vinyl ethers consisting of HCl alone without Lewis acid. This system is a facile metal-free living cationic polymerization using no HCl/Lewis acid but the already adopted complex HCl center dot Et2O. In this study, we investigated the effects of a monomer and ether structure on the polymerization behavior. The monomers are classified into three kinds of monomers: alkyl vinyl ether, vinyl ether with electron-donating groups in the pendant, and vinyl ether with bulky group next to the electron-donating substituent in the pendant. The HCl center dot Et2O systems were applicable for the polymerizations of all vinyl ethers used. However the structure around electron-donating groups in the pendant of monomer affected the polymerizations rate and induction period. The initiation reactions can be successfully achieved using ether effectively dissociating HCl, especially symmetrical ether.