We examine the hygroscopic properties of particles freshly emitted from laboratory biomass burning experiments conducted during the second Fire Lab At Missoula Experiment (FLAME-II). Values of the hygroscopicity parameter, kappa, were derived from both hygroscopic growth measurements and size-resolved (30–300 nm in diameter) cloud condensation nuclei (CCN) measurements for smokes emitted by the open combustion of 24 biomass fuels from the United States and Asia. To analyze the complex cloud condensation nuclei response curves we propose a new inversion scheme that corrects for multiple charge effects without the necessity of prior assumptions about the chemical composition and mixing state of the particles. Kappa varied between 0.02 (weakly hygroscopic) and 0.8 (highly hygroscopic). For individual smokes, kappa was a function of particle size, with 250 nm particles being generally weakly hygroscopic and sub-100 nm particles being more hygroscopic. At any given size the emissions were often externally mixed, showing more and less hygroscopic growth modes and bimodal CCN activation spectra. Comparisons between growth factor-derived and CCN-derived hygroscopicities were consistent when taking this heterogeneity into account. A conceptual model of biomass burning emissions suggests that most particles are CCN active at the point of emission and do not require conversion in the atmosphere to more hygroscopic compositions before they can participate in cloud formation and undergo wet deposition.