The occurrence of hydride-transfer reactions during the cationic polymerization of trioxane was demonstrated, and rate constants were obtained. The donor of hydride ions in the transfer reactions was the monomer. The hydride-transfer reaction was a first-order reaction with respect to the concentration of the monomer, and it was governed, just as polymerization and depolymerization were (Shieh, Y. T.; Chen. S. A. J. Polym. Sci. Part A: Polym. Chem. 1999, 37, 483-492) by morphological changes. The hydride-transfer rate constants were 5 orders of magnitude smaller than those for polymerizations and depolymerizations. The rate constants for the reactions, including the polymerizations, depolymerizations, and hydride transfers, were smaller for the active centers on the solid surface than for those in solution, that is, k(p)' was less than k(p), k(d)' was less than k(d), and k(ht)' was less than k(ht). As a reaction medium, benzene had special effects on the kinetics of the cationic polymerization of trioxane.