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. Therefore, in this paper, a comparative assessment between the total (cT) and non-renewable (cNR) unit 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, the non-renewable unit exergy costs and specific CO2 emissions for the transportation service in all cases analysed are 3.1 to 4.7 times lower compared with conventional fossil fuels (e.g., diesel, gasoline, natural gas and hydrogen). Among the waste upgrade alternatives, methane production is able to maximise the exergy flow rate of products in the transformation stage (52.4-58.6 MW), while hydrogen and electricity production can substantially increase the transportation service in the end-use stage (51.7-52.1%) and the operational revenues (2,706-2,889 EUR/h).