Amongst academics and practitioners working in the fields of urban planning and design, there has been an on-going discussion regarding the relationships between urban morphology and environmental sustainability. A main focus of analysis has been to investigate whether the form of cities and neighbourhoods can be related to their energy efficiency, especially regarding the energy intensity of buildings and transportation. However, to analyse the overall energy performance of urban systems, both the consumption and the generation of resources need to be assessed. In terms of urban environmental sustainability, the potential to generate renewable energy within the city boundaries is a research topic of growing interest, being solar energy one of the main resources available. This study uses neighbourhood-scale statistical models to explore the relationships between aggregated urban form descriptors and the potential to harvest solar energy within the city. Different possible scenarios of urban morphology in Greater London are analysed and variables of urban form are tested with the aim of increasing the solar energy potential of neighbourhoods. Results show that by optimising combinations of up to eight variables of urban form the solar irradiation of roofs could be increased by ca. 9%, while that of façades could increase by up to 45%. Furthermore, based on these results, a series of trade-offs needed for the optimisation of conflicting variables is unveiled. Finally, some recommendations for design strategies are offered with the aim of helping urban planners and designers improve the solar energy potential of new or existing urban areas.