Rhodamine B (RB) nanoparticles entrapped in hybrid glasses show enhanced fluorescent emission (similar to 220-fold larger than that of single RB molecules) thanks to the configuration control of the self-assembled aggregates that form the supramolecular architecture of the nanoparticles. The fluorescence performance reported in this work is around 1 order of magnitude larger than that recently reported for fluorescent Nile Red nanoparticles. The fluorescence enhancement results from the use of a highly efficient fluorescent dye such RB and the formation of larger nanoparticles. Note that the later implies the presence of a large number of emitting centers involved in the fluorescence emission.