Carbonaceous particles originating from biomass burning can account for a large fraction of organic aerosols in a local environment. Presently, their composition, physical and chemical properties, as well as their environmental effects are largely unknown. Tar balls, a distinct type of highly spherical carbonaceous biomass burn particles, have been observed in a number of field campaigns. The Yosemite Aerosol Characterization Study that took place in summer 2002 occurred during an active fire season in the western United States; tar balls collected during this field campaign are described in this article. Scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure spectroscopy are used to determine the shape, structure, and size-dependent chemical composition of similar to 150 individual spherical particles ranging in size from 0.15 to 1.2 mu m. The elemental composition of tar balls is similar to 55% atomic carbon and similar to 45% atomic oxygen. Oxygen is present primarily as carboxylic carbonyls and oxygen-substituted alkyl (O-alkyl-C) functional groups, followed by moderate amounts of ketonic carbonyls. The observed chemical composition, density, and carbon functional groups are distinctly different from soot or black carbon and more closely resemble high molecular weight polymeric humic-like substances, which could account for their reported optical properties. A detailed examination of the carboxylic carbonyl and O-alkyl-C functional groups as a function of particle size reveals a thin oxygenated interface layer. The high oxygen content, as well as the presence of water-soluble carboxylic carbonyl groups, could account for the reported hygroscopic properties of tar balls. The presence of the oxygenated layer is attributed to atmospheric processing of biomass burn particles.