Inorganic–organic hybrid latex containing fluoride has been prepared in multistage emulsion polymerization in the presence of nano-SiO₂ particles and alkoxysilane (γ-methacryloxypropyltri(isopropoxy)silane, MAPTIPS). The effects of fluoride and alkoxysilane on the morphologies of composite particles were observed and it was found that the encapsulation may be fulfilled in the presence of dodecafluoroheptyl methacrylate together with MAPTIPS whether using raw SiO₂ particles or modified. The distribution of fluorine in different latex films was measured by X-ray photoelectron spectroscopy. It was indicated that the gradient distribution of fluorine from depth profile in the films may be enhanced by MAPTIPS and encapsulated SiO₂ due to the bidirectional move of MAPTIPS and congregation of SiO₂ on the film surface. Combining the results of XPS with AFM analysis, it was showed that the phase separation between organic and inorganic for encapsulated SiO₂ was lightened, while it was so apparent for raw SiO₂ that the orientation to the surface of fluorine was restrained in the lack of MAPTIPS.