Biorefinery concept is gaining interest as a promising option for enhancing the benefits of biomass in the sugarcane industry. The study assesses the environmental sustainability of sugarcane biorefinery systems expressed in terms of potential environmental impacts. The biorefinery system includes sugarcane cultivation and harvesting, sugarcane milling and by-product utilization i.e. bagasse for steam and electricity, molasses for ethanol, and vinasse for fertilizer and soil conditioner. The results revealed that the improvement of sugarcane cultivation and harvesting practice e.g. green cane production along with integrated utilization of biomass residues through the entire chain would help reduce the environmental impacts of the main products derived from sugarcane e.g. sugar and ethanol. The potential impacts on climate change, acidification, photo-oxidant formation, particulate matter formation and fossil depletion could be reduced by around 38%, 60%, 90%, 63% and 21%, respectively. Hotspots identified from the results of this LCA study can provide the important information for policy makers towards enhancing sustainable sugarcane production in the future. Recommendations for effective implementation of the proposed sugarcane biorefinery options to Thai sugarcane and sugar industries are discussed.