Al/Cs/MDMO-PPV/ITO (where MDMO-PPV stands for poly[2-methoxy-5-(3'-7'-dimethyloctyloxy)-1,4phenylene vinylene] and ITO is indium tin oxide) light-emitting diode (LED) structures, made by physical vapor deposition of Cs on the emissive polymer layer, have been characterized by electroluminescence, current-voltage, and admittance spectroscopy. Deposition of Cs is found to improve the balance between electron and hole currents, enhancing the external electroluminescence efficiency from 0.01 cd A-1 for the bare Al cathode to a maximum of 1.3 cd A-1 for a Cs coverage of only 1.5×1014 atoms/cm2. By combining I-V and admittance spectra with model calculations, in which Cs diffusion profiles are explicitly taken into account, this effect could be attributed to a potential drop at the cathode interface due to a Cs-induced electron donor level 0.61 eV below the lowest unoccupied molecular orbital. In addition, the admittance spectra in the hole-dominated regime are shown to result from space-charge-limited conduction combined with charge relaxation in trap levels. This description allows us to directly determine the carrier mobility, even in the presence of traps. In contrast to recent literature, we demonstrate that there is no need to include dispersive transport in the description of the carrier mobility to explain the excess capacitance that is typically observed in admittance spectra of p-conjugated materials.