Abstract. The atmospheric reactions of halogenated formaldehydes with halogen atoms were investigated by high-accuracy molecular orbital calculation. Our studies showed that compared to X-addition pathway, the H-abstraction pathway was demonstrated to be more preferred to form halogenated formyl radicals and hydrogen halides (HX). In specific areas with abundant halogen atoms, such as the marine boundary layer (MBL), halogenated formyl radical was reacted easily with halogen atoms and finally transformed into HX and CO₂ in the presence of water; otherwise, this radical was degraded to CO₂, halogen gas, and halogenated oxide in the presence of O₂ and halogen atoms. By using the canonical variational transition state theory, the kinetics calculations were performed within a wide atmospheric temperature range of 200–368 K, and theoretical values agreed well with the available experimental data. Under atmospheric conditions, rate constants decreased as altitude increased, and especially the rate constants of halogen atoms reacted with FCHO quickly reduced. The kinetic results showed that although the reactions of halogenated formaldehydes with F atoms occurred more easily than did those with Cl and Br atoms, the two latter reactions were still important atmospheric degradation process, especially in the MBL. The modified Arrhenius equations of rate constants within the atmospheric temperature range were fitted, which helped to understand the established atmospheric model and estimated the contribution of title reactions to atmospheric chemistry pollution.