A novel octavinyl polyhedral oligomeric silsesquioxane/fluorine containing poly (styrene-acrylate) (OvPOSS/FPSA) composite latexes with star-type structure was synthesized by emulsion copolymerization. The structures of OvPOSS/FPSA composite materials were characterized by Fourier Transform Infrared, which indicated that OvPOSS could be grafted onto FPSA latexes by emulsion copolymerization. Transmission electron microscopy images disclosed that FPSA latexes possessed obvious core–shell structure and OvPOSS/FPSA composite latexes probably present star-shape structure. Dynamic light scattering data indicated that the average diameter of OvPOSS/FPSA was slightly larger than that of FPSA, which was probably attributed to the encapsulation of POSS cages. Atomic force microscopy photos illustrated that the grafting reaction had increased the roughness of the composite surface. The water contact angle of composite films was found increasing as the percentage of OvPOSS increasing. Thermogravimetric analysis curves demonstrated that the OvPOSS/FPSA composite films displayed much better thermal stability than that of FPSA.