The invention belongs to the field of preparation of inorganic materials, and particularly relates to a preparation method of hollow rod-shaped MgF2 particles and application thereof to a self-cleaning antireflective film. After the hollow rod-shaped MgF2 particles and SiO2 particles are compounded, a layer of film is plated by a pulling-dipping method, and after the film is dried at 250 DEG C, the superhydrophobic self-cleaning antireflective film of which the maximum light transmittance can reach 97% or above within the range of visible light is obtained.