The problem of global warming is still a major issue, alongside shrinking oil reserves. A great alternative to fossil fuels is offered by biofuels, such as bioethanol from lignocellulosic plants. The sorghum biomass can be effectively used in many industrial directions. It is possible to use every part of this plant; the grain can be used for food production and straw can be used for energy purposes, i.e., for bioethanol. The aim of this study was to analyze the possibilities of bioethanol production from five varieties of sorghum biomass, which is a waste product of seed harvesting. The yields of sorghum cultivars in a three-year vegetation period; the amount of cellulose, hemicellulose, and lignin in the biomass of sorghum; and the amount of ethanol obtained per hectare were evaluated. It was observed that the highest average yield for all cultivars, except GK Emese, was found in the second year of the study. The bioethanol yield per hectare from this biomass was the highest for Sweet Caroline and was 9.48 m3∙ha−1. In addition, significant differences were found in the content of lignin and hemicellulose for the varieties tested in all years of the study and for the content of cellulose in the first and third years. The discussed results were confirmed by detailed statistical analyses, including combined matrices of Pearson correlation coefficients (crp) varieties and cluster analysis. In summary, the usefulness of the biomass of the studied sorghum varieties for the production of bioethanol was demonstrated.