A series of SiO2 microspheres with different particle sizes were prepared by sol-gel method. SiO2@PDA microspheres with different particle sizes were prepared by using polydopamine as black light absorbing material. SiO2@PDA microspheres were deposited on the surface of the white polyester fabric by gravity deposition. The high structural color fabric with high colorfastness was prepared by adding a lab synthesized adhesive poly(glycidyl methacrylate-co-hexafluorobutyl acrylat)-g-polyethylene glycol methacrylate (P(GMA-co-FHBMA)-g-PEGMA). The SiO2 microspheres, SiO2@PDA microspheres and structural color fabrics were characterized by Malvern high sensitive nano-particle size analyzer, SEM Datacolor colorimeter and measuring microscope. The relationship between the amount of dopamine and the particle size, morphology and fabric structure color of SiO2 @ PDA microspheres was investigated. The effect of adhesive dosage on structural color fastness and colouration was studied. The results showed that the SiO2 microspheres prepared in this experiment have uniform particle size and good monodispersity. The particle size of the prepared SiO2@PDA microspheres increased with the increasing of dopamine content, thus to make the structure color of the fabric red-shift. However, the excessive addition of dopamine would make the microspheres rough and reduce the particle size uniformity, monodispersity of the microspheres and the brightness of the structural color. The addition of the P(GMA-co-FHBMA)-g-PEGMA adhesive could inhibit structural color cracking improving the fastness.