By using pyran-containing donor-acceptor dyes as doping molecules in organic light-emitting devices (OLEDs), we scrutinize the effects of charge trapping and polarization induced by the guest molecules in the electro-active host material. Laser dyes 4-(dicyanomethylene)-2-methyl-6-[2-[(julolidin-9-yl)phenyl]ethenyl]-4H-pyran (DCM2) and the novel 4-(dicyanomethylene)-2-methyl-6-[2-[(4-diphenylamino)phenyl]ethenyl]-4H-pyran (DCM-TPA) are used as model compounds. The emission color of these polar dyes depends strongly on doping concentration, which we have attributed to polarization effects induced by the doping molecules themselves. Their frontier orbital energy levels are situated within the bandgap of the tris(8-hydroxyquinoline)aluminum (Alq₃) host matrix and allow the investigation of either electron trapping or both electron and hole trapping. In the case of DCM-TPA doping, we were able to show that electron trapping leads to a partial shift of the recombination zone out of the doped Alq₃ region. To impede charge-recombination processes taking place in the undoped host matrix, a charge-blocking layer efficiently confines the recombination zone inside the doped zone and gives rise to increased luminous efficiency. For a doping concentration of 1 wt.-% we obtain a maximum luminous efficiency of 10.4 cd A^-1. At this doping concentration, the yellow emission spectrum shows excellent color saturation with CIE chromaticity coordinates x, y of 0.49 and 0.50, respectively. In the case of DCM2 the recombination zone is much less affected for the same doping concentrations, which is ascribed to the fact that both electrons and holes are being trapped. The experimental findings are corroborated with a numerical simulation of the doped multilayer devices