A comparative sustainability study of bioethanol production from selected starchy feedstocks that are abundantly available was carried out in this work. This is to ensure the safe, reliable, and efficient production and consumption of fuel-grade bioethanol. The analysis utilised the established economic minimum bioethanol plant capacity of 158,000 m3/annum. The processing flowsheet model utilised was the same for each feedstock. The sustainability study's economic, environmental, and energy perspectives were investigated. The economic and environmental indices were assessed using Superpro Designer and openLCA sustainability software, respectively. Exergy and lost work were subsequently estimated manually with Microsoft Excel. The economic analyses showed that the plants using cassava and sweet potato initially had the highest return on investment (ROI) of 64.41 and 41.96% respectively at a minimum of 80% plants’ capacity utilisation. The break-even point occurs at a bioethanol price of $3.27 per gallon, beyond which positive net present values were obtained for the four processes. The least profitable plant was based on sorghum recording an ROI value of 34.11%. The environmental assessment on the four selected feedstocks showed that the processes based on cassava, corn, sweet potato, and sorghum recorded encouraging global warming potential (GWP) of 0.2452, 0.2067, 2.5261, and 0.2099 kg CO2 equivalent respectively. Cassava and corn emerged as the two most economically viable feedstocks when economic parameters were adjusted to include pollutants emission/discharge costs but with a slight decrease in profitability indices. The lost work analyses showed that distillation columns were the least energy-efficient units in the four bioethanol production routes assessed, recording loss work of about 61, 68, 34, and 49 MW for cassava, sweet potato, corn, and sorghum processing plants respectively. However, the net energy balance (NEB) and energy renewability results of the four production routes showed that the processes utilising the four selected starchy biomass feedstocks are more sustainable compared to fossil fuels.