Hydration of various commercially available magnesia raw materials were studied under hydrothermal conditions. Raw materials were characterized by XRD, XRF, TG/DTA and SEM/EDS methods. Subsequently, they were subjected to hydration test conducted at temperature of 162oC and presuure of 552 kPa according to ASTM C 554-92 standard. The evolution of phase, microstructure and physicochemical behaviour after hydration test were analysed by XRD, DTA/TG and SEM/EDS. The results showed that presence of the specific secondary phases plays a crucial role in preventing MgO grains against the hydration. Merwinite, monticellite, magnesioferrite and srebrnodolskite were found to constitute protector-like phases that inibit hydration process of magnesia.