A novel environmentally benign biphasic system composed of propylene carbonate (PC) and aqueous solution of
p-toluenesulfonic acid (
p-TsOH aq) was designed for the efficient valorization of lignocellulosic bamboo residues, resulting in more than 95.5% of hemicellulose and 97.2% of lignin digested under mild conditions of 130 °C for 1 h. Meanwhile, 91.9% of cellulose was retained with loose structure, followed by 95.8% enzyme hydrolysis yield and 347.9 mg/g of glucose yield. Notably, the synergistic effect between PC and
p-TsOH on efficiency and selectivity was proposed by a control group experiment and subsequently verified, which is believed to be responsible for the simultaneous degradation and separation of lignin and hemicelluloses into oligomeric phenols and pentose, also facilitating subsequent valorization. Furthermore, the novel PC/
p-TsOH aq biphasic system demonstrated excellent retrievability and adaptability to different feedstocks, offering a promising green strategy for the efficient valorization of lignocellulosic biomass in industrial biorefineries.