Due to the low thermo-economic performance of solar ORC plants, several studies are ongoing to investigate the potential merits/demerits of biomass hybridization as a retrofit. Although many of such studies have examined the technical and economic viabilities of various hybrid solar-biomass concepts, due attention has not been directed to the area of their sustainability based on the Second Law of Thermodynamics. This study was aimed at investigating the potential effects of biomass hybridization on the exergetic sustainability of an organic Rankine cycle (ORC) power plant. Design data of an existing solar ORC plant currently operational at Ottana (Italy) were employed for analysis. The referenced ORC plant is rated at about 630 kWe, powered at the moment solely by a concentrated solar power (CSP) field, which integrates linear Fresnel collectors with two-tank thermal energy storage (TES) device. Five different exergetic sustainability indicators were employed in this study to assess the aforementioned ORC plant when fed by hybrid solar-biomass energy resources. Results showed the hybrid plant's destruction factor (DF), exergetic sustainability index (ESI), environmental effect factor (EEF), improvement potential rate (IPR), and recoverability ratio (RECR) of 89.40%, 0.119, 8.435, 4744.8 kW, and 0.89, respectively. Additionally, a comparison of the solar-only and the hybrid solar-biomass schemes revealed that biomass hybridization would improve the exergetic sustainability of the ORC plant. Nevertheless, the high value of IPR obtained suggests that ample opportunities would yet exist to further enhance sustainability indices of the studied ORC plant post biomass hybridization. In sum, biomass hybridization of the solar ORC plant considered in this study would enhance sustainability performance but more opportunities would yet exist to further optimize the system.