Monomer free polystyrene samples, produced by evaporation from a solvent excluding oxygen, show by excitation with UV-light (λ=270 nm) or with β-rays besides the excimer peak at 330 nm (P-peak) an additional fluorescence peak at 390 nm (G-peak). This peak disappears by melting of the sample or admission of air. The influence of additives on the fluorescence spectra was investigated. 1,2-di-(2-pyridyl)-ethylene, an efficient quencner for the first excited singlet state of polystyrene, reduces the P-peak much more than the G-peak. Therefore it is inprobable that the states responsible for the P-and G-peak are excimers of different distance or symmetry of the segmers or excimers with more than 2 segmers participating. The intensity of the G-peak in comparison to the P-peak increases by addition of low concentrations of hexachlorocyclohexane (c<10−5mole/1). The dependence on the structure of the polymer and the influence of the electron scavenger suggests, that the appearance of the G-peak is connected with the existence of electron traps. We assume that the origin of the G-peak is a charge separate state analogous to that proposed by Janssen and Funabashi to explain the luminescence in γ-irradiated alkane glasses.