We have developed a system of solar reflective coatings that can reflect the sunlight then reduce the temperature of coated surface. The base layer material, fluorinated polystyrene-acrylate copolymers water-based emulsion was firstly prepared with hexafluoro butyl methacrylate(HFBA), styrene(St), butyl acrylate(BA), methyl methacrylate (MMA) by pre-emulsion copolymerization method. The effect on copolymerization and emulsion properties were investigated, and the polymerization condition was optimized. A hollow ceramic micro-sphere was used as the main reflective functional fillers in the system. We had a test on the practical heat-insulating properties on a prototype device. The result showed that temperature difference of the surface was reached as 6.5 °C. The new type of reflective coatings also has good stability and durability.