Raspberry-like silica nanospheres were prepared by electrostatic self-assembly of polyelectrolytes and monodisperse silica nanoparticles of two different sizes, and their coatings were fabricated via layer-by-layer assembly with polyelectrolytes and following calcination. The morphology of the raspberry-like silica nanospheres and their coatings were observed by scanning and transmission electron microscopies. The surface properties of these coatings were investigated by measuring their water contact angles, and the results showed that such hierarchically structured coatings had unique superhydrophilic and antifogging properties. Finally, the formation mechanism and the property–structure relationship were discussed in details. Raspberry-like silica nanospheres and their coatings were prepared via a facile layer-by-layer dip-coating approach, and the obtained hierarchically structured coatings demonstrated unique superhydrophilic and antifogging properties.