Abstract The synthesis of 5,5′‐[oxybis(methylene)]bis‐2‐furfural (OBMF) from 5‐hydroxymethylfurfural (5‐HMF) was studied using bulk and alumina‐supported Preyssler heteropolyacids (HPAs). The formation of OBMF was related to the amount of Brønsted acid sites, and the lowest yield of OBMF was obtained with supported HPAs. However, the Lewis acidity of the HPA supported on Al 2 O 3 favored the formation of 2,5‐dimethylfurane. The effects of solvent, catalyst loading, temperature, and reaction time on the selectivity to OBMF from 5‐HMF were studied to optimize OBMF production using bulk Preyssler HPAs; a yield of 84 % to OBMF was obtained at 5 h and 343 K. These results demonstrate that bulk Preyssler HPA is a good candidate for OBMF synthesis under mild reaction conditions.