The need to contain climate change and improve energy security has increased the interest in agricultural biomass as a renewable energy source (RES). Given the complexity of the issue of energy production and its environmental impact, the main objective of this study was to assess the significance and potential of the agriculture of the European Union Member States in terms of the capability of producing renewable energy. Using the multi-criteria TOPSIS (Technique for Order of Preference by Similarity to Ideal Solution) method, we designed a synthetic measure based on several diagnostic characteristics for 2010–2021, obtaining a ranking for EU countries reflecting their agriculture’s RES potential. The research showed that the agricultural sectors with the highest potential for renewable energy production were in the Netherlands, Lithuania, Latvia, and Hungary during the study period. Bulgaria, Denmark, and Spain joined this group in 2021. A comprehensive assessment was conducted using the TOPSIS method to identify the leaders and areas in need of support in leveraging the potential of agriculture for energy in the EU.