Identifying districts’ potential to become Positive Energy Districts (PED) is challenging but strategic since they are considered critical enablers for cities’ carbon neutrality. PEDs are city areas with a positive annual energy balance, achieved primarily through energy efficiency and renewable energy generation while ensuring sufficient energy flexibility. This investigation introduces a methodological framework designed to prioritise and comprehend the potential PED status of diverse districts within a city, drawing upon predetermined criteria and expert insights. The study employs a combination of Decision Making Trial and Evaluation Laboratory (DEMATEL) and Analytic Network Process (ANP) methodologies to scrutinise the city's various districts and the influencing criteria. The method's applicability is tested through to the specific case of Valencia City. The study reveals that the importance of specific criteria in attaining PED varies according to the distinctive attributes of each district. Furthermore, variations emerge based on the perspective and expertise of the contributing experts. The results of this application allowed the selection of the 19 most influential criteria, organised into technical, social, urban, environmental and economic clusters. The two economic criteria (Investement and Grant or projects), one social criterion (Interest or acceptance) and one technical (Potential for retrofitting the buildings), are the most influential overall. The evaluation of the 19 administrative districts of Valencia for each criterion allowed the identification of the districts on the city's outskirts as having the greatest potential to be energy-positive. In conclusion, the proposed methodology aids decision-making in a city's urban energy planning on a district-by-district basis.