Dichlorvos (2,2-dichlorovinyl phosphate, DDVP) is a widely used organophosphorus insecticide. DDVP may be released into the atmosphere, where it may be transported for long distances and undergo chemical transformations. The mechanisms of the atmospheric reactions of DDVP have not been fully understood because of the short lifetime of its oxidized radical intermediates and the extreme difficulty in the detection of these species experimentally. In this paper, we carried out molecular orbital theory calculations for the OH-initiated atmospheric photooxidation of DDVP. The profile of the potential energy surface was constructed, and the possible channels involved in the reaction are discussed. Several energetically favorable reaction pathways are revealed for the first time. The calculated results were compared with the available experimental observations. Four product pathways are energetically feasible for DDVP degradation initiated by OH radicals in the atmosphere and are consistent with the experimentally observed products CCl2O and CO, but the additional products CCl2CHO, (CH3O)2P(O)OH, HO2, and a closed-shell organophosphorus compound denoted P10 are also predicted.