A novel solid p-hydroxybenzenesulfonic acid–formaldehyde resin (SPFR) was prepared via a straightforward hydrothermal method. The catalytic properties of SPFR solid acids were evaluated in the dehydration reaction of fructose and glucose to 5-hydroxymethylfurfural (HMF). SEM, TEM, N2 adsorption–desorption, elemental analysis (EA), thermogravimetric analysis (TGA), and FT-IR were used to explore the effects of catalyst structure and composition on the HMF preparation from fructose. The effects of reaction time and temperature on the dehydration of fructose and glucose were also investigated. An HMF yield as high as 82.6% was achieved from fructose at 140 °C after 30 min, and 33.0% was achieved from glucose at 190 °C in 30 min. Furthermore, the recyclability of SPFR for the HMF production from fructose in 5 cycles was good.
