Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775-1082 K and pressures near 900 Torr using a high repetition rate time of flight mass, spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly, and, it was found that formaldehyde is the sole product of 1,3,5-trioxane dissociation. Reaction rate coefficients were extracted by the best fit to the experimentally measured concentration-time histories. Additionally, high-level quantum chemical and RRKM calculations were employed to study the falloff behavior of 1,3,5-trioxane dissociation. Molecular geometries and frequencies of all species were obtained at the B3LYP/cc-pVTZ, MP2/cc-pVTZ, and MP2/aug-cc-pVDZ levels of theory, whereas the single-point energies the stationary points were calculated using coupled cluster with single and double excitations including the perturbative treatment of triple excitation (CCSD(T)) level of theory. It was found that the dissociation occurs via a concerted mechanism requiring an energy barrier of 48.3 kcal/mol to be overcome. The new experimental data and theoretical calculations serve as a validation and extension of kinetic data published earlier by other groups. Calculated values for the pressure limiting rate coefficient can be expressed as log(10) k(infinity) (s(-1)) = [15.84 - (49.54 (kcal/mol)/2.3RT)] (500-1400 K).