The wetting behavior of superhydrophilic polyelectrolyte brushes was investigated. Reflection interference contrast microscopy demonstrated that the contact angles of water on the polyelectrolyte brushes were extremely low but remained finite in the range of <3 degrees. The presence of water molecules was evident, even outside the macroscopic water droplet. These water molecules were confined to the thin brush layers and contained a highly ordered hydrogen bond network, which was identified as structural water. The presence of the thin film and the structural water changed the surface energies, which prevented the complete wetting of the surface.