Flue gas produced by biomass fuel combustion contains various chlorine-containing substances and is an important factor causing biomass boiler corrosion. The corrosion processes of chlorine, hydrogen chloride and water on iron covered with an intact/damaged oxide film were investigated under the high temperature of 1300 K through reactive molecular dynamics simulation. The results show that the diffusion processes of oxygen and chlorine are similar and can be divided into three stages: rapid diffusion, continuous diffusion, and no oxide film (stable). Oxygen diffusion in Fe2O3 into a pure iron layer is the main cause of gas corrosion in iron/iron oxide systems. A complete oxide film can hinder iron corrosion by chlorine and hydrogen chloride. Damage in an oxide film significantly affects oxygen and chlorine diffusion and iron corrosion. However, such influence is gradually reduced. The integrity of a protective film is the key to alleviating corrosion. Water facilitates the dissociation of chlorine and hydrogen chloride, and it reacts with iron at high temperatures to enhance corrosion. This study improves the understanding of the iron oxide/iron corrosion from chlorine-containing gases from a microscopic perspective and is of great significance to metal corrosion protection and biomass combustion technologies.