This work presents a systematic procedure for the synthesis of multiproduct processes based on biomass towards the production of a portfolio of products. It is a hybrid scheme that combines the use of metrics and superstructure optimization approach for the selection of products and processing stages towards making the most of the biomass including the foodenergy nexus. A case study of interest, the olive tree is used to present the results of the methodology since olive oil, antioxidants, energy and other by-products can be obtained from the leaves, the tree residues and the olives.