Hybrid solar–biomass organic Rankine cycle (ORC) systems represent a promising avenue for sustainable energy production by combining abundant but intermittent solar energy with the reliable biomass energy. This study conducts a detailed thermodynamic and economic assessment of these hybrid systems, focusing on their potential to enhance energy efficiency and reduce greenhouse gas emissions. The study also evaluates the performance of various working fluids, identifying optimal configurations for different operating conditions. A key finding is that the hybrid system, with an optimized solar–biomass ratio, achieves up to a 21 to 31% improvement in efficiency and a 33% reduction in levelized cost of electricity (LCOE) compared to solar-only systems. Additionally, the study examines case studies of real-world applications, offering insights into the scalability and cost-effectiveness of these systems in regions with high solar irradiation and biomass availability. These results underline the need for continued technological innovation and policy support to promote widespread adoption of hybrid ORC systems, particularly in the context of global decarbonization efforts.