Achieving net-zero emissions in urban environments requires a detailed understanding of how urban form affects the integration of renewable energy systems. Solar energy offers a viable strategy for urban decarbonization by enabling on-site electricity generation, particularly in high-density areas with concentrated energy demand. However, complex urban morphology, especially in mixed-use developments, can significantly constrain solar access on rooftops and façades. This study investigates the relationship between urban morphological parameters and solar energy potential in Da’an District, Taipei, a compact mid-rise urban area representative of mature East Asian cities. Key variables were extracted using Geographic Information System (GIS), including block size, shape, orientation, building coverage ratio (BCR), floor area ratio (FAR), average building height, and height variation. Solar radiation per floor area was used as the target variable to represent photovoltaic (PV) generation intensity. A Random Forest (RF) model was applied to evaluate the relative importance of these parameters, and SHapley Additive exPlanations (SHAP) analysis was used to quantify their individual contributions. This approach enables the identification of key urban form drivers of solar performance and provides a scalable, data-driven method for assessing solar suitability in complex urban environments. The findings offer practical insights for urban planners by identifying morphological features that most influence solar access and informing strategies for energy-efficient retrofits and net-zero urban development.