Biomass samples from a diverse range of ecosystems were burned in the Intermountain Fire Sciences Laboratory open combustion facility. Midinfrared spectra of the nascent emissions were acquired at several heights above the fires with a Fourier transform infrared spectrometer (FTIR) coupled to an open multipass cell. In this report, the results from smoldering combustion during 24 fires are presented including production of carbon dioxide, carbon monoxide, methane, ethene, ethyne, propene, formaldehyde, 2-hydroxyethanal, methanol, phenol, acetic acid, formic acid, ammonia, hydrogen cyanide, and carbonyl sulfide. These were the dominant products observed, and many have significant influence on atmospheric chemistry at the local, regional, and global scale. Included in these results are the first optical, in situ measurements of smoke composition from fires in grasses, hardwoods, and organic soils. About one half of the detected organic emissions arose from fuel pyrolysis which produces white smoke rich in oxygenated organic compounds. These compounds deserve more attention in the assessment of fire impacts on the atmosphere. The compound 2-hydroxyethanal is a significant component of the smoke, and it is reported here for the first time as a product of fires. Most of the observed alkane and ammonia production accompanied visible glowing combustion. NH3 is normally the major nitrogen-containing emission detected from smoldering combustion of biomass, but from some smoldering organic soils, HCN was dominant. Tar condensed on cool surfaces below the fires accounting for ∼1% of the biomass burned, but it was enriched in N by a factor of 6–7 over the parent material, and its possible role in postfire nutrient cycling should be further investigated.