As a key anti-degradation barrier that restricts the biotransformation of lignocellulose, the presence of lignin usually severely affects the quality of the extracted xylo-oligosaccharides (XOS). Herein, this study proposed a practical route to improve the quality and antioxidant activity of XOS extracted from lignocellulosic biomass via selective removal of lignin. The highest delignification of 92.6% was successfully achieved with 8% sodium chlorite at 75°C for 2 h. An ideal hemicellulose sample with a purity of 86.1% was obtained by selective removal of lignin. A high-quality XOS sample with a purity of 96.3%, a yield of 77.4%, and a color value of 814 was obtained by separating and purifying the enzymatic hydrolysate. Antioxidant activity assay showed that the highest radical scavenging activity of XOS was 87.3%. Importantly, this study provide a feasible and effective route for the lignocellulosic biomass utilization strategy based on the selective removal of lignin.