Detailed theoretical investigation has been performed on the mechanism, kinetics and thermochemistry of the gas phase reactions of CF3CH2OCH3 (HFE-263fb2) with OH radicals using ab-initio and DFT methods. Reaction profiles are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels, respectively. Our calculations reveal that hydrogen abstraction from the CH2 group is thermodynamically and kinetically more facile than that from the CH3 group. Using group-balanced isodesmic reactions, the standard enthalpies of formation for CF3CH2OCH3 and radicals (CF3CHOCH3 and CF3CH2OCH2) are also reported for the first time. The calculated bond dissociation energies for the CH bonds are in good agreement with experimental results. At 298K, the calculated total rate coefficient for CF3CH2OCH3+OH reactions is found to be in good agreement with the experimental results. The atmospheric fate of the alkoxy radicals, CF3CH(O)OCH3 and CF3CH2OCH2O are also investigated for the first time using the same level of theory. Out of three plausible decomposition channels, our results clearly point out that reaction with O2 is not the dominant path leading to the formation of CF3C(O)OCH3 for the decomposition of CF3CH(O)OCH3 radical in the atmosphere. This is in accord with the recent report of Osterstrom et al. [CPL 524 (2012) 32] but found to be in contradiction with experimental finding of Oyaro et al. [JPCA 109 (2005) 337].