Abstract: Poly(styrene-acrylonitrile) emulsion particles with positive charges on the surface were synthesized by emulsion polymerization using cationic surfactant octotyltrimethyl ammonium chloride (OTAC) as emulsifier.The suspension of montmorillonite was slowly dropped into the emulsion.Through the interaction between the negative charges on the montmorillonite layers and the cations on the surface of poly(styrene-acrylonitrile) particles, the montmorillonite layers and emulsion particles could assemble and absorb on each other by themselves.The change of δ voltage and particle size of the emulsion during the process of dropping was characterized, which demonstrated that the emulsion particles and montmorillonite layers absorbed on each other by the electrovalent bond and an intersectional structure was formed in the complex emulsion.Poly(styrene-acrylonitrile)/ montmorillonite nanocomposite was obtained after coagulation.The structure of nanocomposite was characterized with XRD and TEM.The results indicated that montmorillonite was exfoliated into layers with a thickness of several nanometers and uniformly dispersed in the polymer matrix.