Biomass burning emits a wide range of carbona-ceous particles into the atmosphere and has negative impacts on human health and the Earth's radiative balance. Nonvolatile spherical organic aerosol particles, commonly known as tar balls, represent one of the most abundant particles in aged biomass burning smoke. However, the detailed molecular level composition of ambient tar balls is largely unknown but critical to assess their environmental impacts. Ambient aerosol samples collected during a wildfire event, which were similar to 90% tar balls by number fraction, were analyzed using ultrahigh-resolution Orbitrap Elite mass spectrometry with four complementary ionization modes. Our results show the molecular composition of tar balls to be complex, composed of over 10,000 molecular formulas. Model estimated saturation mass concentrations and relative humidity-dependent glass-transition temperatures were consistent with low volatility and solid morphology as expected for tar balls. Room-temperature evaporation kinetics showed that these particles retained similar to 90% of their volume after 24 h of evaporation. The molecular complexity detected here signifies a continuum of carbonaceous species, ranging from C-3 to C-45 with continuous ranges of oxygenation and hydrogen saturation for each Cn. Approximately 24% of molecular formulas were estimated to be highly aromatic, which could indicate chemical compounds with negative health effects and which may contribute to visible light absorption. The carbon continuum observed here has significant implications for the molecular characterization of atmospheric organic matter. The level of complexity detected here should not be ignored in future studies, and we demonstrate that multiple analytical methods may be required to suitably interpret this complexity on a molecular level.