Photovoltaic-green roofs (PV-GRs) represent an innovative solution combining renewable energy generation with urban sustainability. However, their performance is influenced by various interconnected factors that require critical analysis. This study examines key elements affecting the efficiency and synergy of PV-GRs, including climatic conditions, plant species selection, substrate properties, and photovoltaic panel placement. The interaction between the green roof’s cooling effect and the photovoltaic system’s efficiency is explored, alongside the impacts of shading, water retention, and maintenance practices. Challenges such as system integration, cost considerations, and long-term performance variability are also discussed. By evaluating these factors, the study provides insights into optimizing PV-GR designs for enhanced energy output and environmental benefits, promoting their adoption in urban areas.