This study presents a comprehensive analysis of Africa's potential to produce bioethanol from agricultural residues and its environmental impact. The relentless consumption of fossil fuels and associated environmental challenges necessitate a shift toward sustainable energy sources, with bioethanol emerging as a promising alternative. This study evaluates the capacity for bioethanol generation from agricultural residues in Africa, considering its land, water, and carbon footprints. Based on data from 85 primary agricultural residues across Africa, approximately 102.256 Gt of fresh agricultural residue is estimated to be available in Africa, translating to approximately 62.117 Gt of dry-weight material. This significant capacity indicates a substantial potential for bioethanol production in Africa, corresponding to a net output of 207.127 EJ. The coproduction potential of bioethanol and electricity are also highlighted, with electricity accounting for 8.016 % of the total net bioethanol energy production. However, the environmental impact of bioethanol production varies across African nations, suggesting the need for optimization and sustainable practices. Additionally, the study discusses the challenges encountered in the bioethanol sector, including the sustainability of production, emission reduction, technological and financial constraints, and the broader context of biomass usage. In conclusion, although bioethanol production from agricultural residues is a promising alternative for Africa's energy sector, it should be realized only after a multifaceted assessment involving technological, economic, policy, and environmental considerations.