In the present paper some main directions in mechanochemical synthesis are developed, based on the mechano‐destructive process induced under different conditions in homo‐ and heterochain solid polymers (polyethylene, cellulose and derivatives, polyesters and polyamides). The fact is known that the elastic energy conferred to crystalline amorphous polymers focuses on structural and composition defects distributed statistically, causing molecular ruptures of the homolytic type which generate nascent microcracks propagating and increasing within the solid leading finally to a fracture. The nascent microcrack represents in fact the existence within small volumes of a number of active macroradicals (or of a number of reactive functional groups after the stabilization of the destruction fragments) capable of reacting with appropriate chemical reagents existing in the working medium. On this basis became possible the initiation of graft polymerization, block copolymerization, polycondensation, and complexing reactions. The concentration of the elastic energy not on molecular underlayers but on metallic surfaces, even when these are the reaction vessel walls, leads to the formation of active centers of a particular type, capable of initiating homo‐ or copolymerization reactions.