The aeronautical sector faces challenges in meeting its net-zero ambition by 2050. To achieve this target, much effort has been devoted to exploring sustainable aviation fuels (SAF). Accordingly, we evaluated the technical performance of potential SAF production in an integrated first- and second-generation sugarcane biorefinery focusing on Brazil. The CO2 equivalent and the renewability exergy indexes were used to assess environmental performance and impact throughout the supply chain. In addition, exergy efficiency (ηB) and average unitary exergy costs (AUEC) were used as complementary metrics to carry out a multi-criteria approach to determine the overall performance of the biorefinery pathways. The production capacity assumed for this analysis covers 10% of the fuel demand in 2020 at the international Brazilian airports of São Paulo and Rio de Janeiro, leading to a base capacity of 210 kt jet fuel/y. The process design includes sugarcane bagasse and straw as the feedstock of the biochemical processes, including diverse pre-treatment methods to convert lignocellulosic resources to biojet fuel, and lignin upgrade alternatives (cogeneration, fast pyrolysis, and gasification Fischer-Tropsch). The environmental analysis for all scenarios shows a GHG reduction potential due to a decrease of up to 30% in the CO2 equivalent exergy base emissions compared to fossil-based jet fuel.