This work focuses on the hydration of four calcium aluminate phases – C3A, C12A7, CA and CA2. Above all, the influence of particle size and method of preparation on hydration behaviour were studied. Influence of these factors on hydration products were also investigated. Calcium aluminates were prepared by solid state synthesis and amorphous citrate method. Both methods were described in detail. The particle size was determined by laser diffraction. Isothermic calorimetry was used to investigate the process of hydration. Hydration products were identified by X-ray diffraction analysis and simultaneous thermogravimetric and differential thermal analysis.