In this article, the feasibility of preparing chlorinated ethylene vinyl acetate copolymer (CEVA) in gas–solid phase is investigated. Furthermore, the structure of the chlorination product and its performance as a coating material are also analyzed. Both the molecular structure and crystallinity of the product are well studied with various characterization methods, including 1H-NMR, Fourier transform infrared, gel permeation chromatography, differential scanning calorimeter, and so forth. The results show that the chlorination of EVA in gas–solid phase is feasible and the chlorine content of CEVA can be made over 60%. It is also found that when the chlorine content is low, chlorination can easily occur in ethylene section but rarely happens in vinyl acetate section. Nevertheless, when the chlorine content of CEVA rises over 35%, CH in the vinyl acetate section is also found chlorinated. The removal of hydrogen chloride is induced during chlorination, producing double bonds in the main chain. Besides, the trace of CCl2 structure can also be found in the chain of CEVA. After chlorination, the crystallization will change and is negatively correlated with chlorine content. As the film forming material for coating, CEVA has its best performance with 50% chlorine content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41093.