In our recent work [Bunkin et al. Water 2013, 4, 129-154] it was first obtained that the water layer, having a size of several tens of micrometers and being adjacent to the swollen Nafion interface, is characterized by enhanced optical density; the refractive index of water at the interface is 1.46. Furthermore, the birefringence effect was observed in this layer. To explain these results, it has been hypothesized that because of "disentangling" of charged polymer chains from the Nafion surface toward the bulk of water, a photonic crystal close to the surface is formed [Bunkin et al. Water 2013, 4, 129-154]. In this paper, we describe experiments with laser-stimulated luminescence from dry and swollen Nafion. It was shown in the experiment with dry Nafion that the apparatus function of our experimental setup (Green's function) is well-described by a Gaussian profile. It was obtained that a highly concentrated colloidal suspension of Nafion particles with a steep spatial boundary is formed in the water layer adjacent to the interface. The volume density of the Nafion particles as a function of the distance from the Nafion interface was found. These findings can be considered indirect confirmation of the previously formulated photonic crystal hypothesis [Bunkin et al. Water 2013, 4, 129-154].