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The catalytic transformation of furfuryl alcohol and hexose into value-added chemicals have been investigated with a series of polymer-based catalysts including poly(styrenesulfonic acid) (PSS), graphite oxide-doped poly(styrenesulfonic acid) (PSS-GO), and graphite-doped poly(-styrenesulfonic acid) (PSS-C). It is found that the selective conversion of furfuryl alcohol to methyl levulinate (MLE) was successfully per-formed with PSS as the catalyst, in which a 96.4％yield is attained in methanol solvent. Moreover, the efficient dehydration of D-fructose to produce 5-hydroxymethylfurfural (HMF) has also been achieved using PSS-GO as the catalyst, where a 76.5％yield of HMF was obtained in N-methylpyrrodinone solvent. The effects of reaction temperature, time and solvent were investigated. Furthermore, the used catalysts have been respectively characterized by XRD, TG, FTIR, SEM and TEM techniques to reveal the physical properties and structures of these polymeric catalytic materials.