The polymerization of alkyl vinyl ethers initiated by hydrogen iodide and iodine catalyst has been studied in detail. The polymerization showed living behavior in nonpolar solvents at low (-15°) temperatures as reported earlier by others. The observed rate of polymerization under the reaction conditions was linearly dependent on the initial concentration of hydrogen iodide and iodine, respectively. However, the monomer concentration did not influence the rate of polymerization (apparent zero order). From the observed rate equation, two possible reaction schemes were proposed and attempts were made to distinguish them by using UV/visible spectroscopy and13C-NMR spectroscopy. In both schemes a reversible interaction between monomer and an iodine molecule was postulated as a necessary elemental reaction to fit the observed expression for rate of polymerization. From the spectroscopic analysis results, the interaction between the iodide compound (chain end) and the iodine molecule seems to be very weak compared to the interaction between monomer and the iodine molecule.