Monodispersed polystyrene colloidal particles containing fluorine were synthesized by two-stage semicontinuous emulsion polymerization in the presence of trifluoroethyl methacrylate (F(3)MA) as a functional co-monomer. And then the colloidal crystal films were fabricated quickly from aqueous colloidal solutions by the vertical deposition method at certain temperature and humidity. The chemical components and thermal property of colloidal particles were determined by Fourier-transform infrared spectrometry and differential scanning calorimetry, respectively. The size and morphology of the particles were characterized by scanning electron microscopy (SEM). The surface element distribution of colloidal crystal films was measured by X-ray photoelectron spectroscopy (XPS). The optical property and water contact angles of the colloidal crystal films were investigated. When the concentration of F(3)MA relative to the total content of monomers was 2.5%, the size and the coefficient of variation (C-v) of colloidal particles were 211 nm and 4.2%, respectively. The colloidal crystal film exhibited high water-contact angles (121.3 degrees). The surface analysis by using XPS revealed that the fluorinated components preferentially enriched at the colloidal crystal film surface. (C) 2008 Wiley Periodicals, Inc.