As the most representative functional sugar, the application areas and market demands of xylo-oligosaccharides (XOS) have been expanding year by year. Owing to the complex structure of corn stalk (CS), XOS obtained from CS are accompanied by problems such as low purity and high color value, which degrade the product. To improve the quality of XOS from CS, the enzymatic hydrolysis was precipitated by acid; then, the ethanol elution concentration was systematically investigated after optimizing the adsorption conditions. The results showed that the purity of XOS was increased to 87.28% from 67.31%, and the color value was decreased to 1050 from 4682 when the acid precipitation pH was 2. On the basis of acid precipitation, if the corresponding optimal conditions of XOS adsorption and elution were used, the highest purity of XOS was 97.87% obtained, with the lowest color value, 780, which reached the standard of the commercial XOS.