The contribution of PCDD/PCDF emissions from soil during open burning of biomass was examined. Mass labelled PCDD/PCDF was added to soil containing native PCDD/PCDF and biomass was laid out on this soil and burnt, simulating sugarcane trash and forest fires. Smoke samples were collected using a high volume portable field sampler. After each fire the concentration of all mass labelled PCDD/PCDF congeners in the surface soil decreased, however, the concentration of some native 2,3,7,8 substituted congeners increased, indicating that formation was occurring. Mass labelled PCDD/PCDF congeners were detected in all ash samples, mean 2.8 pg g−1 (range 0.5–8 pg g−1), demonstrating release from the soil. Additionally, mass labelled PCDD/PCDF congeners were detected in all air samples mean 1.2 μg (t fuel)−1 (range 0.2–2.0 μg (t fuel)−1), again demonstrating release from the soil. Native 2,3,7,8 substituted congeners detected in the air samples were dominated (in terms of contribution to total congener mass) by Cl8DD (90% for forest litter and 77% for sugarcane). The major contributor to TEQ of emissions from both forest litter and sugarcane was 1, 2, 3, 7, 8-Cl5DD (40–64% and 57–75%, respectively). These results demonstrate that release of PCDD/PCDF from soil to air and land occurs during open burning of biomass when soil temperatures are sufficiently elevated.