Kinetics of isobutyl vinyl ether polymerization initiated by Ph3C+SbCl6− in CH2Cl2 were reexamined by using adiabatic calorimetry and spectrophotometry as previously applied to p‐methoxystyrene polymerization. Consumptions of monomer and trityl hexachloroantimonate were followed simultaneously in the temperature range −40° to +25°C. Initiation appeared to be slow (incomplete initiator consumption at temperature equal to or lower than 0°C), and significant transfer and termination processes prevent the system to be considered as “living” (active‐centers concentration goes through a maximum during the polymerization). The initiation step was found to be first‐order with respect to monomer and to initiator, and an overall second‐order with respect to monomer was found for the polymerization. Initiation parameters were separately determined, whereas propagation, transfer to monomer, and termination parameters were computed on the basis of a unimolecular termination process, this leads, for example, to the following rate constants at 0°C and to the activation energies of corresponding reactions: .

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