In this contribution the literature relevant to characterization of polyelectrolytes, polyelectrolyte complexes and hydrogels using luminescence spectroscopy is reviewed. A brief introduction to the fundamentals of luminescence is followed by a description of the various types of spectroscopic studies which may be used to characterize hydrogels. In addition to experiments based upon the addition of a viscosity, temperature- or polarity-sensitive fluorescent probe to characterize the local environment, experiments and techniques based upon luminescence quenching, fluorescence polarization, phosphorescence depolarization and excimer fluorescence are discussed. This review succinctly describes the utility of luminescence spectroscopy in the characterization of hydrogel systems, with a focus on recent developments in the characterization of hydrogels and polyelectrolyte complexes.