We report on electromodulation (EM) spectroscopy studies of phosphorescent multi-layer organic light-emitting diodes (OLEDs) that are processed from solution. Compared to conventional single-layer OLEDs, they comprise an additional layer of a crosslinkable, oxetane-functionalized triphenylamine-dimer (XTPD) that is inserted between the PEDOT:PSS anode and the emissive layer. Devices with optimized stack architecture feature reduced operating voltages and reach a current efficiency approaching 40 cd/A-twice as much as the corresponding single-layer device. Using EM measurements, we quantify the electric field in the XTPD layer and the emissive layer of such a multi-layer OLED and also measure the average electric field in a single-layer reference device. By comparing the dependence of the internal field on the applied voltage for devices with and without the XTPD layer, we find that in the device containing the XTPD layer there is an increased accumulation of electrons at the anode side of the emissive layer. This accumulation enhances the recombination probability and supports the injection of holes into the emissive layer which explains the observed efficiency improvement and reduction in operating voltage compared to conventional single-layer OLEDs. © 2009 Springer-Verlag.