The invention belongs to the field of preparation of organic / inorganic nano-composite microspheres, and particularly relates to a preparation method of 
polymer / ZnO / SiO2 nano-composite microspheres. The preparation method includes the steps that firstly, vinyl monomers and organic 
siloxane are copolymerized through a 
miniemulsion polymerization method to prepare 
polymer microspheres carrying active 
silicon hydroxyl on the surfaces; then, an organic amine alkali source acts with active 
silicon hydroxyl on the surfaces of the 
polymer microspheres to generate nano-ZnO on the surfaces of the polymer microspheres in situ, and polymer / ZnO nano-composite microspheres are prepared; finally, the polymer / ZnO / SiO2 nano-composite microspheres are prepared in situ with a 
sol-
gel method under the induced 
nucleation effect of nano-ZnO particles on the surfaces of the polymer microspheres. The obtained polymer / ZnO / SiO2 nano-composite microspheres are controllable in particle size and morphology, and solve the problems that nano-ZnO particles are prone to agglomeration and poor in 
dispersity; the nano-composite microspheres can be applied to the fields of paint, adhesives, ink, plastic, rubber, fibers and the like as multifunctional filler, and can bring excellent mechanical performance, 
ultraviolet resistance, antistatic performance, durability and the like to the materials.