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Increasing awareness about sustainability has compelled the recent researchers to explore different methods for evaluation. Conventionally the sustainability of a process was majorly dependent on the economics feasibility. Recently need of incorporation of environmental and social concerns in overall sustainability assessment has been realized. Authors in their prior work has published a framework for performing sustainability assessment of biomass processing enterprises. The present work is on selection of sugarcane valorization pathways based on the sustainability index using the same framework. Six alternative routes are compared based on their economic, environment and social criteria. Life cycle assessment of each process is performed as per ISO 14040/44 to evaluate the environmental criteria. Integrated method of value function (MIVES) is used for consolidation of different indicators and criteria. Amongst the process alternatives considered for assessment, 1G2G ethanol route is observed to have highest sustainability index (0.864) owing to relatively lower environmental impact whereas first generation butanol production route (1GRS) had the least sustainability index of 0.090 on account of decreased yield and less products. Sensitivity analysis performed on the model showed no significant change in the ranking of the alternatives.