The efficiency of using in the charge of SHS-mixtures wollastonite “active” additives of micron size activated and modified by different organic compounds as a result of mechanochemical treatment(MCT) is considered. The structure, composition and morphology of modified particles of wollastonite depending on the conditions of MCT in mills-activators of dynamic action are studied. During SHS of composition metal-oxide materials, wollastonite particles play the role of the centre of the mixture combustion site, provide the local increase of temperature, change thermodynamic characteristics of the sample synthesis process as a whole and contribute to formation of nanostructurized SHS-ceramics with high strength and dielectric characteristics.