Biomass burning is a significant anthropogenic source of air pollution, including the preharvest burning of sugar cane. These burn events result in atmospheric emissions, including semivolatile organic compounds, that may have adverse impacts on air quality and human health on a local, regional, and even a global scale. Gaseous and particulate polycyclic aromatic hydrocarbon (PAH) emissions from various sugar cane burn events in the province of Kwa‐Zulu Natal in South Africa were simultaneously sampled using a portable denuder sampling technology, consisting of a quartz fiber filter sandwiched between two polydimethylsiloxane multichannel traps. Total gas and particle phase PAH concentrations ranged from 0.05 to 9.85 µg m–3 per individual burn event, and nine PAHs were quantified. Over 85% of all PAHs were found to exist in the gas phase, with smaller two‐ and three‐ring PAHs, primarily naphthalene, 1‐methyl naphthalene, and acenaphthylene, being the most dominant and causing the majority of variance between the burn sites. The PAH profiles differed between the different burn events at different sites, emphasizing the significant influence that the crop variety, prevailing weather conditions, and geographical location has on the type and number of pollutants emitted. The potential carcinogenicity of the PAH exposure was estimated based on toxic equivalency factors that showed varying risk potentials per burn event, with the highest value of 5.97 ng m–3. Environ Toxicol Chem 2023;42:778–792. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.