The semiconducting-polymer/injecting-electrode heterojunction plays a crucial part in the operation of organic solid state devices. In polymer light-emitting diodes (LEDs), a common fundamental structure employed is Indium-Tin-Oxide/Polymer/Al. However, in order to fabricate efficient devices, alterations to this basic structure have to be carried out. The insertion of thin layers, between the electrodes and the emitting polymer, has been shown to greatly enhance LED performance, although the physical mechanisms underlying this effect remain unclear. Here, we use electro-absorption measurements of the built-in potential to monitor shifts in the barrier height at the electrode/polymer interface. We demonstrate that the main advantage brought about by inter-layers, such as poly(ethylenedioxythiophene)/poly(styrene sulphonic acid) (PEDOT:PSS) at the anode and Ca, LiF and CsF at the cathode, is a marked reduction of the barrier to carrier injection. The electro- absorption results also correlate with the electroluminescent characteristics of the LEDs.