This study evaluates bushfire smoke as a workplace hazard for firefighters by characterising its chemical composition and potential health risks in Western Australia. Portable Fourier Transform Infrared (FTIR) spectrometry was used to measure airborne chemical concentrations at prescribed burns across five regions, including peat (acid sulphate) fire events. Samples were collected during both flaming and smouldering phases, as well as in perceived “clear” air resting zones. Results indicated that carbon monoxide (CO) was the dominant gas, reaching concentrations of 205 ppm at the fire front, followed by nitrogen monoxide (26 ppm) and methane (19 ppm). Peat fires produced distinct profiles, with ammonia (21.5 ppm) and sulphur dioxide (9.5 ppm) concentrations higher than those observed in typical bushfires. Smouldering phases emitted higher chemical concentrations than flaming phases 75% of the time. Even clear air zones contained measurable chemicals, with CO levels averaging 18 ppm, suggesting that firefighters are not free from exposure during rest periods. These findings highlight the need for fit-for-purpose respiratory protective equipment (RPE) and improved rest protocols to minimise exposure. The study underscores the importance of comprehensive health monitoring programs for firefighters to mitigate long-term health risks.