As part of the Fire Lab at Missoula Experiments (FLAME) in 2006–2007, we examined hygroscopic properties of particles emitted from open combustion of 33 select biomass fuels. Measurements of humidification growth factors for subsaturated water relative humidity (RH) conditions were made with a hygroscopic tandem differential mobility analyzer (HTDMA) for dry particle sizes of 50, 100 and 250 nm. Results were then fit to a single-parameter model to obtain the hygroscopicity parameter, κ. Particles in freshly emitted biomass smoke exhibited a wide range of hygroscopicity (individual modes with 0<κ<1.0), spanning a range from the hygroscopicity of fresh diesel soot emissions to that of pure inorganic salts commonly found in the ambient aerosol. Smoke aerosols dominated by carbonaceous species typically had a unimodal growth factor with corresponding mean κ=0.1 (range of 0<κ<0.4). Those with a substantial inorganic mass fraction typically separated into less- and more-hygroscopic modes at high RH, the latter with mean κ=0.4 (range of 0.1<κ<1). The bimodal κ distributions were indicative of smoke chemical heterogeneity at a single particle size, whereas heterogeneity as a function of size was indicated by typically decreasing κ values with increasing dry particle diameters. Hygroscopicity varied strongly with biomass fuel type and, to a lesser extent, with combustion conditions. Among the most hygroscopic smokes were those from palmetto, rice straw, and sawgrass, while smoke particles from coniferous species such as spruces, firs, pines, and duffs were among the least hygroscopic. Overall, hygroscopicity decreased with increasing ratios of total carbon to inorganic ions as measured in PM<sub>2.5</sub> filter samples. Despite aerosol heterogeneity, reconstructions of κ using PM<sub>2.5</sub> bulk chemical composition data fell along a 1:1 line with measured ensemble κ values.