5‐hydroxymethylfurfural (HMF) is an important bio‐based platform chemical for liquid fuel production. Herein, efficient conversion of cellulose to HMF in NaHSO4/ZrO2/H2O‐THF biphasic system was investigated with a high HMF yield up to 86.5%. In the co‐catalytic system, H+ ions given from NaHSO4 was promotive to all steps of the cellulose‐to‐HMF conversion; abundant alkaline sites of ZrO2 was particularly favorable to the glucose‐to‐fructose isomerization. The accelerated conversion of glucose as well as the fast extraction of HMF from aqueous phase to tetrahydrofuran (THF) phase, favored the inhibition of humins which was generated from condensation between glucose and HMF. Only a trace amount of humins over ZrO2 was detected after reaction, which guaranteed the reusability of ZrO2 in six running experiments without any post‐treatment. The good reusability of ZrO2, the low ‐cost of NaHSO4, and the biomass‐derived THF were advantageous for potential industrial application.