Sub-Saharan Africa is a hotspot for biomass burning (BB)-derived carbonaceous aerosols, including light-absorbing organic (brown) carbon (BrC). However, the chemically complex nature of BrC in BB aerosols from this region is not fully understood. We generated smoke in a chamber through smoldering combustion of common sub-Saharan African biomass fuels (hardwoods, cow dung, savanna grass, and leaves). We quantified aethalometer-based, real-time light-absorption properties of BrC-containing organic-rich BB aerosols, accounting for variations in wavelength, fuel type, relative humidity, and photochemical aging conditions. In filter samples collected from the chamber and Botswana in the winter, we identified 182 BrC species, classified into lignin pyrolysis products, nitroaromatics, coumarins, stilbenes, and flavonoids. Using an extensive set of standards, we determined species-specific mass and emission factors. Our analysis revealed a linear relationship between the combined BrC species contribution to chamber-measured BB aerosol mass (0.4-14%) and the mass-absorption cross-section at 370 nm (0.2-2.2 m2 g-1). Hierarchical clustering resolved key molecular-level components from the BrC matrix, with photochemically aged emissions from leaf and cow-dung burning showing BrC fingerprints similar to those found in Botswana aerosols. These quantitative findings could potentially help refine climate model predictions, aid in source apportionment, and inform effective air quality management policies for human health and the global climate.