In very high gravity (VHG) ethanol fermentation, the rheological properties of native cassava significantly influence heat and mass transfer, mixing energy, and, thus, the yield of all steps. This study investigated the effect of cassava varieties and their harvest times on starch liquefaction, saccharification, and fermentation. The genotype correlation of the starch properties was revealed for the most suitable cassava varieties. First, the starch content, amylose content, total reducing sugar from liquefaction and saccharification, pasting properties, and ethanol yields of six cassava varieties (Huay Bong 60, Hanatee, Kasetsart 50, Pirun 1, Pirun 2, and Rayong 11) at 6‐, 9‐, 12‐, and 15‐month harvest times were evaluated. The amylose content increased significantly from the 6th to the 12th month but slightly decreased at the 15th month. It was observed that the starch content contributed to a more substantial influence on the change in peak viscosity than on the amylose content. Ethanol fermentation using Saccharomyces cerevisiae TISTR5606 showed that the Rayong 11 variety at the 15‐month harvest time provided the highest ethanol concentration of 104.7 ± 4.1 g L−1 and an ethanol yield of 0.4 ± 0.1 g ethanol g−1 reducing sugar, which corresponded to 74.5% of the theoretical yield.