AbstractLewisite is a representative chemical warfare agent that contains arsenic. Thermal decomposition is an essential method for Lewisite destruction, and appropriate destruction conditions can enhance the environmental friendliness of this method by minimizing the hazards of destruction products. In this study, the variation of Lewisite during pyrolysis and incineration was calculated, with particular emphasis on the evolution behaviors of arsenic and chloride with temperature, pressure, and molar ratio. The main products identified during pyrolysis were HCl(g), C, As, and AsCl3(g). Under anoxic conditions, AsCl3(g) and As were the dominant species. In oxygen‐enriched conditions, arsenic existed primarily as AsCl3(g), As2O5, As2O4, and AsOCl. Below 600 °C, arsenic predominantly existed in high valence forms such as As2O5. Above 600 °C, the binding capacity of chlorine and arsenic was stronger than that of oxygen, resulting in an AsCl3(g) molar fraction exceeding 75 % at 1200 °C. The primary chlorides in oxygen‐enriched conditions were Cl2(g), HCl(g), AsCl3(g), and Cl(g). Lower incineration temperatures (around 500 °C), sufficient oxygen conditions (molar ratio above 4 : 1), and positive pressures were conducive to reducing the toxicity of destruction products. The results are in good agreement with the experimental data.