Porous silica films with a refractive index varying from 1.44 to 1.15 were prepared and applied to realize a double-layer broadband AR coating. The porous silica films were obtained using tetraethylorthosilicate (TEOS) as precursor and a binary template as porogen which was composed of cetyltrimethylammonium bromide (CTAB) and polypropylene glycol (PPG). The molar ratio of the two templates was optimized, and a hypothetical mechanism for the cooperative assembly of silicates with the binary template system was proposed. The two layers had the same skeleton despite different porosity with the top layer much more porous than the bottom one. The double-layer double-wavelength AR coating had excellent optical properties with transmittances of 99.6% and 99.8% at 532 nm and 1064 nm, respectively.