The electronic processes responsible for charge transport and electroluminescence in multilayered organic light emitting diodes (OLEDs) are very sensitive to the properties of the organic heterojunction. In particular, the height of the energy barrier affects the way in which electrons and holes meet at the heterojunction, the way in which the barrier is crossed, and the probability for photon creation. We investigate these aspects experimentally using a family of OLED devices in which different hole transporting materials are used in otherwise identical device architectures to vary the interfacial hole barrier over a wide energy range. We find that the quantum efficiency of the device is maximum for low-energy barriers and drops for high barrier values where a redshifted electroluminescence spectrum is observed. This shift is attributed to exciplex generation at the heterojunction. The contributions of exciton and exciplex annihilation in radiative and nonradiative channels to the charge flow within the heterojunction region are separated and quantified.