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Prescribed fires can be used as a forest management tool to reduce the severity of wildfires. Thus, over prolonged and repeated periods, firefighters are exposed to toxic air contaminants. This work consisted in collecting and analysing smoke released by typical Mediterranean vegetation during prescribed burning. Sampling was performed at five active zones on the island of Corsica. Seventy‐nine compounds were identified: volatile organic compounds and semi‐volatile organic compounds, including polycyclic aromatic hydrocarbons. Depending on exposure levels, the toxins present in smoke may cause short‐term or long‐term damage to firefighters’ health. The dangerous compounds emitted, benzene, toluene, ethylbenzene and xylenes, were quantified. Their concentrations varied as a function of the study site. These variations were due to the intrinsic and extrinsic characteristics of the fire site (e.g. plant species, fire intensity and wind). Our results show that benzene concentration is high during prescribed burning, close to the exposure limit value or short‐term exposure limit. Benzene can be considered as a toxicity tracer for prescribed burning because its concentration was above the exposure limit value at all the study sites. The authors suggest that respirators should be used to protect staff during prescribed burning operations.