The 'samples of vulcanized rubber compounds with natural rubber INR) and styrene-butadiene rubber (SBR) were prepared. The surface chlorination of samples was performed by immersion of strips in aqueous solution of sodium hypochlorite and in hydrochloric acid in dependence of time and in temperature range from 2O'C to 80'C. The changes of chemical structures, thermal stability and morphological properties of chlorinated vulcanizates were recorded by IR-FMIR spectroscopy, differential scanning calorimetry IDSC) I thermogravimetric analysis ITGA), wide angle X-ray diffraction (WAXD) and scanning electron microscopy (SEMI. Extremely heterogeneous complex mechanisms of chlorination and parallel degradation processes in dependence on time and temperature above all were indicated and compared to NR and SBR vulcanizates. At higher temperatures the structural changes in elastomeric matrix in connection with selective separation and surface migration of multicomponent filler due to agressive media were observed.