Based on the constructed CCSD(T)/cc-pVTZ//M06-2X/aug-cc-pVTZ potential energy surface, the detailed kinetics of the desflurane (CF3CHFOCHF2) + Cl/OH reactions was investigated using canonical transition state theory (TST) with corrections of the hindered internal rotation and tunneling treatments. The suggested rate constants, namely k(Cl) (T)= 8.76 x 10(-21) x T-3.2 x exp(-1961 K/T) and k(OH) (T)= 1.19 x 10(-23) x T-3.7 x exp (-481 K/T) (cm(3).molecule(-1).s(-1)) in the temperature range of 200-2000 K, are in good agreement with experimental data. Moreover, the subsequent unimolecular reactions of the desflurane radicals were also investigated under the atmospheric conditions.