The solid-state photopolymerization of octadecyl vinyl ether was verified occur in rotator phase, and the stability of octadecyl vinyl ether in rotator phases was explained through the study of its electrostatic surface potential. Four binary systems were constructed by mixing the octadecyl vinyl ether with four normal alcohols (the carbon numbers are 12, 14, 16 and 18). The phase behaviors and the kinetics of photopolymerization of four binary systems were studied by using differential scanning calorimeter and real-time Fourier transform infrared spectroscopy. Alcohols are usually regarded as a kind of inhibitor for cationic polymerization in liquid state. However, in rotator phase photopolymerization, the conversions of octadecyl vinyl ether that mixed with octadecyl alcohol (83%) or hexadecyl alcohol (81%) were higher than that of pure octadecyl vinyl ether (47%). This phenomenon was explained from the aspect of two-dimensional solid-state chain propagation.