Monodisperse hollow silica nanospheres have been prepared by using a polystyrene nanosphere template-assistant approach and their potential as antireflection (AR) coatings for window applications has been discussed. The as-prepared hollow silica nanospheres have a typical inner diameter of 200 nm and a shell thickness of 15–20 nm. The AR effect over the ultraviolet-visible-near infrared spectral region has been observed for the hollow silica nanospheres, with a minimized reflection of about 5.2 % at 500 nm, compared to 8.5 % of a plain float glass substrate. By modifying the structural features of the hollow silica nanospheres, their AR properties can be further enhanced.