Poly(glycidyloxypropyl)silsesquioxane (PGPS) was successfully synthesized by hydrolysis and polycondensation using the nitrogen flow method. A poly(3-(2,3-dihydroxypropoxypropyl)silsesquioxane) (PSQ-OH) film was prepared via two routes. In route A, PSQ-OH was prepared by the hydrolysis of the epoxy group of PGPS in an aqueous hydrochloric acid (HCl)/tetrahydrofuran solution, affording a diol group; then, PSQ-OH was coated on a glass substrate and heated. The antifogging performance of the PSQ-OH film was evaluated in terms of water uptake (WU) and scratch resistance. The obtained PSQ-OH film exhibited a low WU of 5% and a scratch resistance of 1.6. In route B, PGPS was coated on a glass substrate and immersed in a 0.5 mol/L aqueous sulfuric acid solution for 1-15 h at room temperature, producing a diol group. The solid-state 13C nuclear magnetic resonance spectrum indicated that the epoxy group was completely hydrolyzed after immersion for 15 h. The WU of the PSQ-OH film prepared via route B increased from 5 to 19% with the increase in the immersion time and was higher than that of the PSQ-OH film prepared via route A. The PSQ-OH film on a glass substrate retained transparency under water vapor exposure at 60 °C. The PSQ-OH film prepared via route B exhibited a high scratch resistance of 2.7-3.6, similar to that of a poly(3-(2-aminoethylaminopropyl)silsesquioxane) film. The scratch resistance of the PSQ-OH film was 5-7 times higher than that of the poly(vinyl alcohol) film. The PSQ-OH film was uniform with no pinholes and cracks. The PSQ-OH film was transparent and colorless and exhibited a high transmittance of >90% in the wavelength range of 400-800 nm. Overall, the prepared PSQ-OH film exhibits good antifogging, transparency, and mechanical properties.