After exposure to ionizing radiation, trioxane polymerizes rapidly at temperatures between 50 and 60°C. The nature of the molecular motions involved in this solid‐state reaction is not clear. Line narrowing in nuclear magnetic resonance absorption has been reported as one indication of such motions. No related dielectric loss peaks were found in trioxane at temperatures from −180 to 55°C and frequencies from 1 to 10 000 Hz. Ionic conductivity is large above room temperature and it may play an important role in this polymerization reaction.