A new silica antireflective coating with improved hydrophobicity and optical stability in a vacuum is obtained by a two-step route. Firstly, silica sols are prepared with a sol-gel process, in which tetraethyl orthosilicate is utilized as a precursor. And by introduction of fluorine containing glycol into the sols, the porosity of silica particles and surface polarity of the coatings are decreased. Afterward, coatings are constructed with low surface roughness by modification of PMBA-PMMA. The coatings retain transmission of up to 99.6%, and laser damage threshold of about 50 J/cm2 at a wavelength of 532 nm (1-on-1, 10 ns).