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Herein, an ionic liquid/water (IL/w) system was developed to separate hemicelluloses from the chemical pulp with enhanced efficiency by employing xylanase. In the traditional IL/w process, when the water content was in the range 20-15%, the extraction of hemicelluloses was 71–80%. However, the highly efficient hemicelluloses removal was always accompanied with an increased cellulose loss. In this regard, xylanase (X) pretreatment was introduced to facilitate the IL/w process for improving the separation selectivity/efficiency of the hemicelluloses. In the case of the IL/w-20 (water content is 20%) procedure, X 30 (30 mg/g xylanase) pretreatment could increase hemicelluloses removal from 71 to 78%, while the separation selectivity increased from 11.0 to 43.8. Additionally, X pretreatment also reduced IL usage/charge to achieve the same degree of hemicelluloses removal. [ABSTRACT FROM AUTHOR]