The thermal decomposition of di-tert-butyl peroxide has been studied in the presence of carbon dioxide at total pressures from 0.05 to 15 atm and temperatures from 90–130 °C. The first-order rate constant for the decomposition is independent of total pressure in this range, with Arrhenius parameters E = 37.8 ± 0.3 kcal/mole and log A(s−1) = 15.8+0.2. A reevaluation of previous data on this reaction leads us to recommend E = 37.78 ± 0.06 kcal/mole and log A(s−1) = 15.80 ± 0.03 over the temperature range 90–350 °C; extension of this range to higher temperatures using a shock tube would be worthwhile.