Görgeyite, K2Ca5(SO4)6··H2O, is a very rare monoclinic double salt found in evaporites related to the slightly more common mineral syngenite. At 1 atmosphere with increasing external temperature from 25 to 150 °C, the following succession of minerals was formed: first gypsum and K2O, followed at 100 °C by görgeyite. Changes in concentration at 150 °C due to evaporation resulted in the formation of syngenite and finally arcanite. Under hydrothermal conditions, the succession is syngenite at 50 °C, followed by görgyeite at 100 and 150 °C. Increasing the synthesis time at 100 °C and 1 atmosphere showed that initially gypsum was formed, later being replaced by görgeyite. Finally görgeyite was replaced by syngenite, indicating that görgeyite is a metastable phase under these conditions. Under hydrothermal conditions, syngenite plus a small amount of gypsum was formed, after two days being replaced by görgeyite. No further changes were observed with increasing time. Pure görgeyite showed elongated crystals approximately 500 to 1000 μ m in length. The infrared and Raman spectra are mainly showing the vibrational modes of the sulfate groups and the crystal water (structural water). Water is characterized by OH-stretching modes at 3526 and 3577 cm−1 , OH-bending modes at 1615 and 1647 cm−1 , and an OH-libration mode at 876 cm−1 . The sulfate ν1 mode is weak in the infrared but showed strong bands at 1005 and 1013 cm−1 in the Raman spectrum. The ν2 mode also showed strong bands in the Raman spectrum at 433, 440, 457, and 480 cm−1 . The ν3 mode is characterized by a complex set of bands in both infrared and Raman spectra around 1150 cm−1 , whereas ν4 is found at 650 cm−1.