Electrical impedance measurements on poly-p-phenylene-vinylene (PPV) light-emitting diodes in the frequency range between 100 Hz and 10 MHz are reported. A significant difference can be revealed between the device characteristics of light-emitting diodes eliminated on indium-tin-oxide (ITO) and those of other high-work-function metals (e.g., Au). Thermal conversion of the precursor polymer on ITO substrates results in ap-type doping of the conjugated polymer PPV. Hence, devices in the configuration ITO/PPV/Al display Schottky behavior, which can be modeled by a simple equivalent circuit of two RC elements in series, representing a bulk and a junction region. The low-frequency device capacitance displays a pronounced voltage dependence and, from a detailed analysis, the ionized acceptor concentrationNA,the diffusion potentialVD,and the width of the space charge regionwcan be obtained. Typical values forNAare1016–1017cm−3, and forVDwithin the range 1–1.5 V, resulting in a widthwof the space charge region at zero bias of about 50–150 nm. Via temperature-dependent investigations a transition from ap-type semiconductor Schottky diode at room temperature to a metal/insulator(polymer)/metal structure at lower temperatures is revealed. ©1997 American Institute of Physics.