Abstract Catalytic dehydration of xylose to yield furfural was studied by testing different heteropolyacid‐type catalysts. Preyssler heteropolyacid (HPA‐Preyssler) (H 14 [NaP 5 W 30 O 110 ]) was the most efficient. Under the optimal reaction conditions, xylose was dehydrated into furfural with 73% of yield and 95% of selectivity using DMSO as solvent at 140 °C for 4 h. The HPA‐Preyssler catalyst also exhibited good catalytic activity in the dehydration of fructose and glucose to yield 5‐hydroxymethylfurfural (HMF). Thus, from fructose a yield and selectivity to HMF of 97% and 98%, respectively, was obtained in just 10 min, while from glucose, 91% of conversion and 23% of yield were obtained after 9 h. An easy and efficient methodology for the recovery and reuse of HPA‐Preyssler in at least six reaction cycles without appreciable loss of its initial catalytic activity is reported.