Recently, mechanochemical synthesis was widely used in preparation of perovskite type of materials, such as BaTiO 3 , PbTiO 3 , PZT, etc. In this work, the possibility of mechanochemical synthesis of CaTiO 3 from different precursors, such as CaCO 3 or CaO and TiO 2 was investigated. Intensive milling of mixture of CaO and TiO 2 , under optimal milling conditions, resulted in synthesis of single phase CaTiO 3 . It was also found that intensive milling of powder mixture containing CaCO 3 and TiO 2 only activate the powders for the sintering process; hence the CaTiO 3 could be obtained at lower temperatures of sintering. To complete reaction of CaTiO 3 formation during milling it is necessary to reduce CO 2 partial pressure, i.e. it is necessary to change the atmosphere inside the vials during milling. In this work, an explanation for difference in milling behavior of different precursors was proposed and discussed.