The current era of energy production from agricultural by-products comprises numerous criteria such as societal, economical, and environmental concerns, which is thought to be difficult, considering the complexities involved. Making the optimum choice among the various classes of organic waste substances with different physio-chemical characteristics based on their appropriateness for pyrolysis is made possible by a ranking system. By using a feasible model, which combines several attributes of decision-making processes, it is possible to select the ideal biomass feedstock from a small number of possibilities based on relevant traits that have an impact on the pyrolysis. In this study, a multi-criteria decision-making (MCDM) technique model based on the weight calculated from the analytical hierarchy process (AHP) tool has been applied to obtain a ranking of different types of agro-waste-derived biomass feedstock. The technique of order preference by similarity to ideal solution (TOPSIS) is used to examine the possibilities of using/utilizing locally available biomass. From this point of view, multi-criteria are explained to obtain yield maximum energy. The suggested approaches are supported by the experimental findings and exhibit a good correlation with one another. Six biomass alternatives and eight evaluation criteria are included in this study. Sawdust is the highest-ranking agricultural waste product with a closeness coefficient score of 0.9 out of the six biomass components that were chosen, followed by apple bagasse with 0.8. The hybrid approach model that has been built can be evaluated and validated for the ranking method using the Euclidian distance-based approximation. This study offers a unique perspective on decision-making, particularly concerning thermo-chemical conversion.