The upgrade of sugarcane industry residues, such as vinasse and bagasse, has a notably potential for large scale production of biofuels in Brazil. Despite this fact, the biomass conversion into either electricity or biofuels requires various energy intensive processes that may drastically affect its technical and environmental competitiveness against their non-renewable counterparts. Accordingly, the mapping of the generation of the process irreversibility and their associated atmospheric emissions may help, by issuing appropriate mitigation tasks, in the reduction of exergy consumption rates and environmental impact. Therefore, in this paper, a comparative assessment between the total (ct) and non-renewable (cnr) exergy costs and specific CO2 emissions (cco2) of the electricity, methane and hydrogen produced from sugarcane vinasse and bagasse is presented and compared with the conventional (fossil fuel-based) supply chains. As a result, a strikingly high average renewable to non-renewable ratio ( cr / cnr ) of 15.2 is estimated for the biofuels derived from the waste upgrade plant. However, due to the larger number of process involved in the conversion of biomass resources, the total exergy costs of biofuels delivered vary from 2.6 to 2.2 times higher in comparison to those derived from fossil fuels. On the other hand, although hydrogen production from sugarcane wastes involves more processes, its unit exergy costs in the end-use stage (transportation service) were found to be the lowest among the studied biofuels, partially due to the higher efficiency of hydrogen-fueled transportation technologies. In general, the production of biofuels and electricity from sugarcane wastes can offer fuels with greatly reduced CO2 specific emissions and low non-renewable energy consumption shares.