SiO2 and Co/SiO2 microspheres was synthesized using TEOS as starting materials by self-assembly processes and used for the photodegradation of GV, ST, and RB under solar light. The samples were characterized by a combination of various physicochemical techniques, such as, diffuse reflectance UV-vis, X-ray diffraction, SEM, and FT-IR. The size distribution of SiO2 and Co/SiO2 microspheres is relatively narrow. The SiO2 for the three dyes have not photoactivity under solar light. By contrast, the Co/SiO2 exhibited high photodegradation yields that is 79%, 45%, and 33% for GV, ST, and RB under solar light, respectively.