5-Hydroxymethylfurfural (5-HMF) and furfural are produced from glucose by using a novel phosphate-doped SnO2 catalyst in GVL/water system. Comparing with the low yield (19.3% 5-HMF, 7.2% furfural) of SnO2 as catalyst, the loading of 15 wt% phosphate on the SnO2 can enhance the yield of 5-HMF (39.2%) and furfural (12.5%) from glucose under same reaction conditions. Furthermore, under the optimal conditions, the results indicate that the phosphated SnO2 catalyst, which contains 5 wt% phosphate, can result in 46.4% yield of 5-HMF and 18.9% yield of furfural at 180 °C for 90 min. The phosphated SnO2 catalysts are characterized by using XRD, TEM, Py-IR, XPS and TPD to reveal their structural, surface, and acid properties. And the enhanced 5-HMF and furfural yield could be attributed to the higher acidity, and the incorporation of phosphate into the framework of SnO2.