The atmospheric reaction of methyldichlor-oacetate (MDCA) with OH radical is studied using electronic structure calculations. Five different pathways were considered for the initial reactions, which results in the formation of alkyl radical of MDCA along with H2O, HOCl, and CH3O circle. Among the five pathways studied, the alpha-carbon atom (-CHCl(2)site) H atom abstraction reaction, which leads to the formation of the alkyl radical intermediate (CCl2C)-C-circle(O)- OCH3 (I1) is found to be more favorable with an energy barrier of 7.3 kcal/mol, and Cl-atom abstraction reaction is having high energy barrier of 21.3 kcal/mol at M06-2X/6-311++G(2df,2p) level. The calculated thermochemical parameters show that except Cl-atom abstraction channel the other initial reaction channels are highly exothermic. The rate constant is calculated for the initial H atom abstraction reactions using canonical variational transition state theory over the temperature range of 278 to 350 K. The Arrhenius plot shows positive temperature dependence for both the reactions. The results from the calculated thermochemical parameters and rate constants show that the formation of the alkyl radical intermediate (I1) is more favorable with the rate constant of 2.07 X 10(-13) cm(3) molecule(-1) s(-1) at 298 K. The calculated atmospheric lifetime of MDCA is 28 days at normal atmospheric OH concentration. The results obtained from secondary reactions show that the major product formed from the oxidation chemistry of MDCA is methyl-2-chloro-2-oxoacetate (or) methyl oxalyl chloride.