Palm-based biorefinery system has gained attention worldwide because of potentially high economic returns. However, environmental impacts also increase with the additional production. Therefore, this study aims to assess the sustainability of (1) current palm-based biorefinery system in Thailand, including cooking oil and biodiesel, and (2) palm-based biorefinery system with value-added products, i.e., succinic acid, lactic acid, bio-hydrogenated diesel (BHD), and epichlorohydrin (ECH) that represent biomaterial, biofuel, and biochemical products, respectively. Accordingly, seven palm-based biorefinery scenarios were designed, and their sustainability was assessed through life cycle assessment (LCA), net energy balance (NEB) and net energy ratio (NER), employment generation, and eco-efficiency. The results revealed that value-added production increased global warming impacts by around 3 – 79% compared with the current system. Although environmental impacts increased due to the additional processes related to the production of the value-added products, total product values also increased, especially for succinic acid, generally leading to higher eco-efficiency values. The current palm-based biorefinery system with succinic acid production had the highest eco-efficiency among all the scenarios considered. The BHD production scenario had the highest NEB and NER because the products were used for energy. Employment generation increased for all the scenarios between 2 – 86% compared with the current system.