Hollow spherical silica film has been used on glass substrates as an antireflective coating, and PAA is one of the common templates for preparing SiO2 films by sol-gel method. In this paper, the effects of polyacrylic acid (PAA) content on the SiO2 films prepared by the sol-gel method were analyzed using TEM, DLS, XRD, IR, SEM, and the transmission spectrum. The sol containing hollow spherical micelles can be prepared well from tetraethyl orthosilicate (TEOS) as raw material and PAA as water-soluble polymer by improved Stober, and template method. With the increase of PAA content, the particle size of hollow spherical silica colloidal particles increases and the quantity decreases. The sol is attached to the surface of the soda lime glass substrate to form a film by dip-coating method. With the increase of withdrawal speed, the transmittance of the glass increases, and with the increase of PAA content from 0.1g to 0.6g, the sample's transmittance decreases first and then increases.