Due to climate change, wildfires are becoming increasingly frequent and intense, leading to substantial production of biomass burning (BB)-derived organic aerosol (BBOA). Although African fires account for over 50% of worldwide BB organic emissions, few studies have systematically analyzed molecular tracers of BBOA in fresh versus photochemically-aged BB emissions representative of African fires. Therefore, using gas chromatography and electron ionization quadrupole mass spectrometry, we analyzed aerosol filter samples collected from both fresh and photochemically-aged BB emissions of six biomass fuel types found in Botswana. The emissions were generated from a furnace mimicking smoldering. For each biomass fuel, 16 known BBOA tracer compounds were quantified and compared between fresh and photochemically-aged BB emissions. Total-suspended atmospheric particulate matter (PM) samples collected from Botswana during fire season were also analyzed. We identified laboratory-generated BBOA constituents (e.g., D-pinitol) that were also found in Botswana PM that could plausibly serve as unique tracers for African BBOA.