Raspberry- and mulberry-like hierarchically structured silica particulate coatings were fabricated via facile in situ layer-by-layer assembly with monodisperse silica nanoparticles (NPs) of two different sizes followed by calcination. Raspberry-like and mulberry-like silica particulate coatings were achieved when the size ratio of two silica particles was 20/200 and 20/70 nm, respectively. The latter coating exhibited good antireflective property. Its maximum transmittance reached as high as 97%, whereas that of the glass substrate is only 91%. The morphologies of the coatings were observed by scanning electron microscopy and atom force microscopy. The surface properties of these coatings were investigated by measuring their water contact angles and the spreading time of water droplet. The results showed that such hierarchically structured coatings had superhydrophilic and antifogging properties.