The poly(isopropylene oxide) glycerolether (PO) modified silica antireflective (AR) coating films were prepared by sol–gel method. The properties of the silica sols and AR films were characterized by particle size analyzer, transmission electron microscope, UV–Vis spectro-photometry, spectroscopic ellipsometer and contact angle measurement. The results show that PO addition has inconspicuous effect on the transmittance of AR coatings; the maximum transmittance reached 99.5%. Thicknesses of films increase and refractive index decrease with increase of PO concentration. The contact angle with water for the silica films with and without PO was 68.5o and 28.5o, respectively, which indicates an increase of hydrophobicity of the modified coating. When the films were placed in 95% relative humidity at room temperature for 30 days, transmittance loss for the unmodified and modified silica films were 2.5 and 0.6% respectively. Moisture-resistance of the film is greatly improved by PO addition.