MIL-101, a chromium-based metal–organic framework, is known for its very large pore size, large surface area and good stability. However, applications of this material in catalysis are still limited. 5-Hydroxymethylfurfural (HMF) has been considered a renewable chemical platform for the production of liquid fuels and fine chemicals. Phosphotungstic acid, H3PW12O40 (PTA), encapsulated in MIL-101 is evaluated as a potential catalyst for the selective dehydration of fructose and glucose to 5-hydroxymethylfurfural. The results demonstrate that PTA/MIL-101 is effective for HMF production from fructose in DMSO and can be reused. This is the first example of the application of a metal–organic framework in carbohydrate dehydration.