Glucose conversion to 5-hydroxymethylfurfural (HMF) generally undergoes catalytic isomerization reaction by Lewis acids followed by the catalytical dehydration to HMF with Bronsted acid. In this work, a sulfonic acid functionalized metal-organic framework MIL-101(Cr)-SO3H containing both Lewis acid and Bronsted acid sites, was examined as the catalyst for -valerolactone-mediated cascade reaction of glucose dehydration into HMF. Under the optimal reaction conditions, the batch heterogeneous reaction gave a HMF yield of 44.9% and selectivity of 45.8%. Reaction kinetics suggested that the glucose isomerization in GVL with 10 wt % water follows the second-order kinetics with an apparent activation energy of 100.9 kJ mol(-1). Continuous reaction in the fixed-bed reactor showed that the catalyst is highly stable and able to provide a steady HMF yield. This work presents a sustainable and green process for catalytic dehydration of biomass-derived carbohydrate to HMF with a bifunctional metal-organic framework. (c) 2016 American Institute of Chemical Engineers AIChE J, 62: 4403-4417, 2016