Purpose -This paper presents a comparative study of scenarios considering different features of the bioethanol supply chain, focusing on the impact of the modal choice and the use of renewable energy on its environmental performance. Currently, the concern with sustainable development leads organizations to improve their production processes in order to reduce greenhouse gas emissions and energy consumption. Therefore, since the bioethanol supply chain is a greater CO2 emitter and depends on several energy sources, it becomes relevant to analyze how to improve this chain regarding environmental issues.Design/methodology/approach -Based on bibliographic and documental research, this paper analyzes the bioethanol supply chain from the sugarcane plantation, in the South Central region of Brazil, to bioethanol exportation (São Sebastião port). The analysis was based on LCA (life cycle analysis) concepts and in a partial application of LCI (life cycle inventory). It was possible to identify which scenario would be the most appropriate considering the total energy consumption, the percentage of renewable energy used and CO2 emissions.Findings -We found that the most appropriate alternative is not the one that uses less energy (roadway combined with pipeline), but the one that uses more renewable energy (roadway using biodiesel). Based on the findings, we concluded that it is possible to improve the environmental performance of the bioethanol supply chain with a combination of renewable energy sources and the selection of modes of transport considered more suitable to this product.Research limitations/implications -In this study, the economic impacts related to the implementation of the two best alternatives were not evaluated (e.g. the amount of investments required to provide biodiesel as the main energy source and to create or expand the infrastructure for pipelines). Another limitation is the scarce availability of data related to supply chain of bioethanol in Brazil.Practical implications -This paper provides information to support the public policies for bioethanol's transport and the public and private managers in the decision-making process.Originality/value -Although there are a lot of studies about the bioethanol supply chain in Brazil, it was not found researches that analyze the impact of modal choice in energy consumption and carbon dioxide emissions considering, at the same time, the life cycle inventory for each transport alternative and different energy sources.