Sulfur hexafluoride SF6 is a very stable molecule with which very few reactions with other molecules have been reported. Here, we report a photochemical reaction of SF6 with water molecules using a matrix-isolation technique, where SF6 and H2O were co-condensed in Xe matrices, and the products were observed using infrared spectroscopy. Irradiation at 193 nm from an ArF excimer laser caused the simultaneous decomposition of SF6 and H2O, which resulted in the production of novel species. Infrared spectra and molecular orbital calculations of the species showed that the product was a SF4HFHOF complex, which consists of hydrogen bonds and charge transfer interaction between S and F atoms. The assignment of the species was confirmed by isotope shifts using D and 18O isotope substitutions.