Hydration processes of the rapid hardening cement clinkers, which were synthesized from domestic alunite for major alumina source, limestone, kaolin and fluorite, were investigated by means of x-ray diffraction analysis, thermal analysis and microscopic observation etc. The clinkers were composed mainly of alite, calcium fluroaluminate (C11A7.CaF2) minerals. While the hydratio processes of the clinkers are altered by concentration of SO3 in the paste, calcium aluminate hydrates such as C4AH13, CAH10 and calcium monosulfate hydrate (C3A.CaSO4.12H2O) are formed at first and then some of them are transformed into ettringite(C3A.3CaSO4.32H2O) within 30~60 min. when the concentration of SO3 in the paste are enough. However the formed ettringite are changed slowly into calcium monosulfate hydrate as the concentration of SO3 become lowered, and the paste is hardened with these close-packed minerals. When the content of SO3 in clinker is so enough, calcium sulfoaluminate hydrates are found without any addition of anhydrite or hemi-hydrite.