Thermally stable nanoporous organosilicate thin films were realized by the microphase separation of pore-generating polymers mixed with an organosilicate matrix to be antireflective coatings (ARCs), for which a thin film with a refractive index (n) of 1.23 for zero reflection is required. The refractive index of such nanoporous organosilicate films can be tuned from 1.39 down to 1.23 by incorporating nanopores within the films. With a nanoporous single layer with n similar to 1.23, the light transmittance of the glass above 99.8% was achieved in the visible range (lambda similar to 550 nm). To overcome the limitation on the narrow wavelength for high transmittance imposed by a single antireflective nanoporous thin film, bilayer thin films with different refractive indices were prepared by placing a high refractive index layer with a refractive index of 1.45 below the nanoporous thin film. UV-vis transmittance of a glass coated with the bilayer films was compared with nanoporous single-layer films and it is demonstrated that the novel broadband antireflection coatings in a wide range of visible wavelength can be easily obtained by the organosilicate bilayer thin films described in this study. Also, ARCs developed in this study demonstrate excellent AR durability owing to the hydrophobic nature of the organosilicate matrix.