Monodisperse polystyrene (PS) colloidal spheres were successfully prepared through emulsifier-free emulsion polymerization by controlling the polymerization reaction time, ionic strength of the system, concentration of the ionic copolymer (sodium p-styrenesulfonate) and other factors. The PS colloidal spheres were assembled into colloidal crystals whose structures were mainly face-centered cubic (fcc) close-packed. Then FDTD method was used to calculate the color-rendering characteristics of the colloidal crystals surface. The calculated results were consistent with the experimental results. Monodisperse polystyrene (PS) colloidal spheres were successfully prepared through emulsifier-free emulsion polymerization by controlling the polymerization reaction time, ionic strength of the system, concentration of the ionic copolymer (sodium p-styrenesulfonate) and other factors. The PS colloidal spheres were assembled into colloidal crystals whose structures were mainly face-centered cubic (fcc) close-packed. Then FDTD method was used to calculate the color-rendering characteristics of the colloidal crystals surface. The calculated results were consistent with the experimental results.