The invention discloses a multilayer nano hollow array antireflection film and a preparation method thereof. The inside of the antireflection film is a multilayer film which has a closed pore structure and is formed by alternate superposition of regularly and compactly arranged nano hollow sphere single-layer silicon dioxide and titanium dioxide, wherein the number of layers is 2-30, and the outermost layer is a compactly closed silicon dioxide film layer. The preparation method comprises the following steps: preparing a sol A from ethyl orthosilicate, deionized water, an acid catalyst and anhydrous ethanol used as raw materials, and adding polystyrene particles to obtain a suspension C; preparing a sol B from tetrabutyl titanate, deionized water, anhydrous ethanol and diethanolamine used as raw materials, and adding polystyrene particles to obtain a suspension D; performing dip coating on cleaned glass in the suspension C, then annealing, further performing dip coating on the coated glass in the suspension D, then annealing, and repeating the operation for 1-25 times; and finally, performing dip coating in the sol A, and then annealing to obtain the antireflection film of which the surface is closed and the inside is a nano hollow array structure.