Rubber/Ca-montmorillonite (Ca-MMT) nanocomposites with exfoliated Ca-MMT layers was prepared by a new preparation method named masterbatch method, in which the masterbatch was prepared by co-coagulating nature rubber latex and bis [3-triethoxysilylpropyl-] tetrasulfide (TESPT) modified Ca-MMT aqueous suspension and then the masterbatch accompanied with carbon black (N220) were used in the system of SBR and ENR. The properties of TESPT in-situ modified Ca-MMT were investigated by Fourier-transform infrared spectroscopy and thermogravimetric analysis. The results showed that the TESPT has reacted with the surface groups of Ca-MMT. The dispersion of the Ca-MMT in masterbatch and vulcanized sample was characterized by X-ray diffraction. The results showed that in the masterbatch an exfoliated structure was obtained and in the vulcanized sample a coexistence of intercalated-exfoliated structure was obtained. The influence of the Ca-MMT loading on the structure and properties of the nanocomposites were studied. It was found that the incorporation of Ca-MMT hindered the vulcanization, improved mechanical properties, thermal properties and aging resistance properties. The dynamic mechanical analysis results showed a decrease of tanδ max when the Ca-MMT is added.