In this work,a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural (EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran (THF).The influence of-SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied.High EMF yields of 67.7％ and 54.2％ could be successively obtained from fructose and inulin in the presence of MIL-101-SO3H (100) at 130℃ for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple.This work provides a new platform by application of porous coordination polymers (PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.