Manufacturing of Al/K/OC1C10 poly(p-phenylene vinylene)/indium–tin–oxide light emitting diode structures by physical vapor deposition of K onto the emissive polymer layer has been characterized by electroluminescence and ion spectroscopy. Varying the deposited K areal density from 3.9×1012 to 1.2×1014 atoms cm–2 the external efficiency rises from 0.01 to 1.2 Cd A–1. Spectra obtained by ion scattering analysis demonstrate the overall absence of K at the polymer outermost surface layer, and diffusion up to a depth of 200 Å. Depth profiles have been derived, and were modeled using an irreversible first order "trapping" reaction. Trapping may stem from confinement of the electron at a conjugated segment, that was donated through charge transfer typical for alkali/-conjugated systems. This study demonstrates that evaporation of low work function metals onto organic systems should not be depicted as simple layered stacking structures. The enhanced electroluminescence with submonolayer K deposition is attributed to the shift of the recombination zone away from the Al cathode, which is demonstrated to prevail over the known exciton quenching mechanism due to the formation of gap states.