Domestic biomass fuels (biofuels) were recently estimated to be the second largest source of carbon emissions from global biomass burning. Wood and charcoal provide approximately 90% and 10% of domestic energy in tropical Africa. In September 2000, we used open-path Fourier transform infrared (OP-FTIR) spectroscopy to quantify 18 of the most abundant trace gases emitted by wood and charcoal cooking fires and an earthen charcoal-making kiln in Zambia. These are the first in situ measurements of an extensive suite of trace gases emitted by tropical biofuel burning. We report emission ratios (ER) and emission factors (EF) for (in order of abundance) carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), acetic acid (CH₃COOH), methanol (CH₃OH), formaldehyde (HCHO), ethene (C₂H₄), ammonia (NH₃), acetylene (C₂H₂), nitric oxide (NO), ethane (C₂H₆), phenol (C₆H₅OH), propene (C₃H₆), formic acid (HCOOH), nitrogen dioxide (NO₂), hydroxyacetaldehyde (HOCH₂CHO), and furan (C₄H₄O). Compared to previous work, our emissions of organic acids and NH₃ are 3–6.5 times larger. Another significant finding is that reactive oxygenated organic compounds account for 70–80% of the total nonmethane organic compounds (NMOC). For most compounds, the combined emissions from charcoal production and charcoal burning are larger than the emissions from wood fires by factors of 3–10 per unit mass of fuel burned and ∼2 per unit energy released. We estimate that Zambian savanna fires produce more annual CO₂, HCOOH, and NO_x than Zambian biofuel use by factors of 2.5, 1.7, and 5, respectively. However, biofuels contribute larger annual emissions of CH₄, CH₃OH, C₂H₂, CH₃COOH, HCHO, and NH₃ by factors of 5.1, 3.9, 2.7, 2.4, 2.2, and 2.0, respectively. Annual CO and C₂H₄ emissions are approximately equal from both sources. Coupling our data with recent estimates of global biofuel consumption implies that global biomass burning emissions for several compounds are significantly larger than previously reported. Biofuel emissions are produced year-round, disperse differently than savanna fire emissions, and could strongly impact the tropical troposphere.