Despite the recent need for sustainable energy resources, bioenergy gained its spotlight in the 2000s. Sugarcane is a significant crop in terms of sugar and energy capacity, and it can be an alternative energy source to mitigate the effects of climate change. Bioenergy production from sugarcane in Brazil is one of the most efficient options. This production lends a centrality to biofuels’ importance in confronting climate change effects. The present article reviews the Brazilian history of this crop as a biofuel source, focusing on plants as a biomass. We highlight the historical changes related to scientific, technological, industrial, and environmental advances since the beginning of the 20th century. We describe how creating governmental institutes and disseminating scientific knowledge strengthened public policies that led Brazil to occupy leadership positions in producing, distributing, and using bioenergy throughout the country. The compiled data show the improvements and the new approaches needed to improve ethanol sugarcane use. We performed a bibliometric analysis to evaluate Brazilian science’s contribution to this process compared to other countries. Brazil’s history of science and investment in sugarcane biofuel development for transportation may be divided into two phases: ethanol-only and flex-fuel cars. A third phase is starting, directed to the SAF and ethanol-to-hydrogen era.