This report introduces the biotechnological valorization potential indicator (BVPI) concept, a metric to measure the degree of suitability of lignocellulosic materials to be used as feedstock in a biorefinery framework. This indicator groups the impact of the main factors influencing upgrade-ability, both the biological/chemical nature of the materials, and the economical, technological and geographical factors. The BVPI was applied to the identification of the most relevant opportunities and constraints pertaining to the lignocellulosic by-products from the Portuguese agro-industrial cluster. Several by-products were identified with a high valorization potential, e.g., rice husks, brewery's spent grain, tomato pomace, carob pulp, de-alcoholized grape bagasse, and extracted olive bagasse, that would greatly benefit from the further development of specific biotechnology processes, specifically concerning the upgrade of their hemicellulosic fraction.