Duckweeds are promising potential sources for bioethanol production due to their high starch content and fast growth rate. We assessed the potential for four species, Landoltia punctata, Lemna aequinoctialis, Spirodela polyrrhiza, and Wolffia arrhiza, for bioethanol production. We also optimized a possible production procedure, which must include saccharification to convert starch to soluble sugars that can serve as a substrate for fermentation. Duckweeds were cultivated on 10% Hoagland solution for 12 days, harvested, dried, homogenized, and dissolved in solutions that were tested as substrates for bioethanol production by the yeast Saccharomyces cerevisiae. First, we optimized the saccharification process, including the ideal ratio of the enzyme used to convert starch into simple sugars. The greatest starch-to-sugar conversion was obtained when the α-amylase and amyloglucosidase was 2:1 (v/v) and with a 24 h incubation period at 50 °C. After saccharification, the solutions were incubated with the yeast, S. cerevisiae. The fermentation process was carried out for 48 h with 10% (v/v) yeast inoculum. The ethanol content was maximal approximately 24 h after the start of incubation, and the sugars and protein were minimal, with little change over the next 24 h. The final ethanol concentration obtained were 0.19, 0.17, 0.19, and 0.16 g ethanol/g dry biomass for L. punctata, L. aequinoctialis, S. polyrrhiza, and W. arrhiza respectively. We suggest that these four species of duckweed have the potential to serve sources of bioethanol and hope that the procedure we have optimized proves useful in the endeavour.