A novel polydivinylbenzene polymeric material containing water-tolerant SO₂NHSO₂C₄F₉ with 2 equivalents of Cr(III) was explored as a catalyst of the one-pot conversion of glucose to 5-hydroxymethylfurfural (HMF) in a biphasic system. Stable 59–57% yields of HMF were achieved throughout 12 cycles over the bifunctional material. Dynamic analysis showed that Cr(III) essentially promoted the isomerization process of glucose to fructose. The material featured integral hydrophobicity, which, with the water-tolerance of SO₂NHSO₂C₄F₉, contributed to its excellent recyclability.