A theoretical study on the kinetic and thermochemistry of the reactions of CH3C(O)OCH3 with Cl atoms is performed using DFT and ab initio methods. The formation of pre and post-reactive complexes indicates an indirect hydrogen-abstraction reaction. The calculated total rate coefficient value k(Cl) = 2.61 x 10(-12) cm(-3) molecule(-1) s(-1) is in good agreement with the experimental value of k(Cl) = 2.79 x 10(-12) cm(3) molecule(-1) s(-1) at 298 K. Our calculations suggest that the H abstraction from -OCH3 group is kinetically and thermodynamically more favorable than the -CH3C(O) group. The atmospheric lifetime of CH3C(O)OCH3 is found to be 44 days. (C) 2014 Elsevier B.V. All rights reserved.