The demand for biofuels has been rising, which has led developing countries to focus on production of feedstocks for biodiesel and bioethanol production. This has caused concerns for the impacts on food security, food prices and environmental sustainability. This paper examines a hypothetical case of cassava-based bioethanol production in southern Mali, assessing its environmental, economic and social sustainability. Results demonstrate that environmental sustainability of cassava-based bioethanol production depends on the ‘baseline’ chosen: Compared to the situation before the decline in cotton production 10 years ago, the carbon stocks will increase. However, if compared to the current situation, where considerable carbon stocks have accumulated in fallow fields, the loss of carbon will be substantial. Increased cassava production will create greater incomes and better temporal distribution of labour input. Analysis of the significance of current cassava production for food security shows that bioethanol production should be based on the attiéké variety of cassava, thereby avoiding interference with the important role of the bonouma in assuring food security in northern Mali. The key factor determining the economic feasibility is whether local farmers will be willing to supply cassava at a realistic price. The results indicate that this is likely to be the case.