In this study, we show that the fluorous alcohol hexafluoroisopropanol (HFIP) can act as a superior solvent for the in situ extraction of 5‐hydroxymethylfurfural (HMF) from an aqueous reaction system. HFIP has a far higher partition coefficient for HMF than common extraction solvents such as methyl isobutyl ketone (MIBK) and n‐butanol and has a significantly lower boiling point of 58–59 °C. In a system containing fructose, HCl as the catalyst, and HFIP as the extraction solvent, a high HMF yield of 89 % is achieved, which is far better than the HMF yields in common MIBK/butanol extraction systems. HFIP extracts HMF from the reaction phase without extraction of the fructose educt. In addition, the aqueous catalyst phase can be reused.