Conversion of carbohydrates to 5-hydroxymethylfurfural (HMF) will provide a new step toward achieving renewable biomass-based chemicals and fuels platform. Recently, the excellent yield of HMF (91.0%) in dimethyl sulfoxide (DMSO) catalyzed by sulfonated carbon was demonstrated, but the separation of HMF from the reaction mixture remains challenging because of the high boiling point of DMSO. As a solution, herein, low boiling point solvent tetrahydrofuran (THF) mixed with DMSO was used for the fructose dehydration and high yield of HMF (98.0%) was still obtained. Besides, the stability of the sulfonated carbonaceous catalyst was also confirmed. More importantly, HMF from the reaction solution was successfully separated by using simple extraction method, and high purity of HMF (ca. 96.4%) was obtained. Compared with pure DMSO solvent, the combination of low boiling point THF with DMSO not only gives higher yield of HMF, but also improves the separation efficiency and reduces environmental risk.