This paper focuses on the optimisation of an efficient extraction process for cellulose and lignin from rice straw waste from the Albufera of Valencia using the steam explosion method. This method is particularly pertinent given the environmental and economic challenges posed by the current disposal practices of agricultural waste. The technique comprises a high-temperature cooking stage followed by instantaneous decompression, effectively altering the biomass’s physical and chemical properties to enhance its surface area and porosity. Our adaptation of the steam explosion technique specifically addresses the challenges of rice straw waste, marking a significant departure from previous applications. This innovation is crucial in addressing the urgent need for more sustainable waste management practices, as it effectively deconstructs the lignocellulosic matrix of rice straw. This facilitates the selective extraction of cellulose at a 70% efficiency, with a 20% yield and the subsequent recovery of lignin. The results of this study are significant for sustainable biomaterial production, offering novel insights into optimising these crucial biomass components. By refining the process and focusing on critical parameters, our work advances the application of steam explosion methods for agricultural waste, enhancing efficiency and sustainability. By utilising rice straw biowaste, this research not only proposes a solution to a pressing environmental issue but also demonstrates the potential to create new market opportunities, increase the economic value for rice producers, and significantly reduce the environmental footprint of existing waste disposal methods. The holistic and ecological approach of this study underscores the vital need for innovative strategies in agricultural waste management, positioning the valorisation of rice straw waste as a key component in the pursuit of environmental sustainability.