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Biomass burning (BB) is a major source of aerosols and black carbon, thereby exerting an important impact on climate and air quality. Levoglucosan is the most well-recognized organic marker compound of BB and has been used to quantitatively assess BB's contribution to ambient aerosols. However, little is known about levoglucosan's evaporation under atmospheric conditions, primarily due to the uncertainty of its effective saturation vapor concentration ( C *) and its unknown activity coefficient (γ), in the complex BB emission matrix. Here, we utilized a thermodenuder to investigate the evaporation of levoglucosan from mixtures with polyethylene glycol (PEG) or BB primary organic aerosol (BBPOA) matrices, respectively. We estimate a pure component log 10 ( C */[μg m -3 ]) of levoglucosan of 1.1 ± 0.1 at 298 K. We reveal that levoglucosan mixed with PEG or BBPOA becomes more volatile than when treated as a single component due to nonideal molecular interactions. Considering that phase separation might occur in such systems, we term γ apparent activity coefficient (γ a ). We estimate log 10 C * and γ a of levoglucosan in BBPOA of 1.8 ± 0.1 and 3.8 ± 0.3, assuming a liquid phase state. Consequently, γ a must be considered to avoid significant underestimation of levoglucosan evaporation via gas-particle partitioning during transport., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)