The X-ray line broadening technique was used to calculate the grain size of MgO at 1023, 1123, 1223 K respectively either in $CO_2$ or during the thermal decomposition of magnesites in air as well as in vacuum. By referring to the conventional grain growth equation, $D^n=kt$, the activation energy and pre-exponential factor for the process in air are gained as 125.8 kJ/mol and $1.56{ imes}10^8;nm^4/s$, respectively. Ranman spectroscopy was employed to study the surface structure of MgO obtained during calcination of magnesite, by which the mechanism of grain growth was analyzed and discussed. It is suggested that a kind of highly reactive MgO is produced during the thermal decomposition of magnesites, which is exactly the reason why the activation energy of the grain growth during the thermal decomposition of magnesite is lower than that of bulk diffusion or surface diffusion.