Due to their lack of effect on the ozone depletion, hydrofluoroethers are considered as potential candidates for third generation refrigerants. In the present work, the mechanisms and kinetics of reaction of the Cl atom with CF(3)CHFOCH(3) and CHF(2)CHFOCF(3) were investigated theoretically using quantum chemical methods and transition state theory. Four reaction pathways for the title reaction were explored. By using conventional transition state theory with Eckart tunneling correction, the rate constants of the title reaction were obtained over the temperature range 200-300 K. Kinetic calculations demonstrate that H-abstraction from the -CH(3) group in CF(3)CHFOCH(3) and H-abstraction from the -CHF2 group in CHF(2)CHFOCF(3) are major reaction pathways, with the barrier heights of the two paths calculated to be -1.04 and 4.33 kcal mol(-1), respectively. However, the contribution of H-abstraction from the -CHFO- group for the two reactions should also be taken into account with increased temperature. At 298 K, the calculated overall rate constants of the reaction of CHF(2)CHFOCF(3) with the Cl atom are 4.27 × 10(-15) cm(3) molecule(-1) s(-1), which is consistent with the experimental value of (1.2 ± 2.0) × 10(-15) cm(3) molecule(-1) s(-1).