This study aimed to characterize and compare the chemical structures, physical properties, and enzymatic hydrolysis rates of five sorghum starches (6B73, 6C21, 6C69, 7R34, and X789) with that of corn starch (B73). Sorghum kernels consisted of 68.7-70.6% starch, more than the B73 corn (67.4%). Sorghum starches displayed higher gelatinization temperatures (66.6-67.4 °C), greater gelatinization enthalpy changes (13.0-14.0 J/g), and greater percentages of retrogradation (60.7-69.1%), but slower enzymatic hydrolysis rates (83.8-87.8% at 48 h) than the B73 corn starch (61.7 °C, 10.1 J/g, 51.5%, and 88.5%, respectively). These differences could result from the sorghum amylopectins consisting of fewer short branch chains (DP 6-12) (12.8-14.0%) than the corn amylopectin (15.0%). The sorghum starches showed greater peak and breakdown viscosities but lower setback viscosities than the B73 corn starch, resulting from the lower amylose content of the sorghum starches. After 96 h of fermentation, most ground sorghums exhibited lower ethanol yields (30.5-31.8%) than the ground B73 corn (31.8%).