The invention relates to the field of anti-reflection technology for the surface of glass, and concretely relates to a nanometer core-shell 
silicon dioxide 
microsphere and a 
composite coating solution which is compounded by the nanometer core-shell 
silicon dioxide microspheres and aluminum 
silicon sol as well as preparation methods thereof. A cation type 
polystyrene emulsion is used as a hard template in order to prepare 
silicon dioxide dispersion liquid with a nanometer core-shell structure, the dispersion liquid and the aluminum silicon 
sol are compounded in order to prepare the 
coating solution for an antireflection film, 
toughening treatment is carried out for the 
coating solution in order to obtain the antireflection film. The raw materials are easy to obtain, and the antireflection film with a hollow structure is prepared by a simple process; pore spaces are arranged in particles and are not arranged in a 
silicon dioxide network, so that high light 
transmittance of the film is guaranteed, the light 
transmittance reaches 94.5% or above, and the 
porosity is high; the film has excellent smudginess resisting performance, the antireflection film and a glass substrate can be firmly combined, and the 
hardness of the film is high; because the surface of the film is compact, the film has good blocking effects for steam 
erosion, good weatherability, and industrialized application values.