We present a systematic investigation of the effects of organic film structure on light emitting diode (LED) performance. Metal/organic film/metal LEDs were fabricated using a five ring, poly(phenylene vinylene) related oligomer as the active layer. The structure of the vacuum evaporated oligomer films was varied from amorphous to polycrystalline by changing the substrate temperature during deposition. The intrinsic properties of the oligomer films and the LED performance were measured. The measured intrinsic film properties include: optical absorption, photoluminescence (PL) spectra, PL lifetime, PL efficiency, and effective carrier mobility. The measured device characteristics include current–voltage, capacitance–voltage, electroluminescence (EL) efficiency, and the contact metal/organic film Schottky barrier heights. The optical absorption and PL properties of the films are weakly dependent on film structure but the effective carrier mobility decreases with increasing crystallinity. The EL quantum efficiency decreases by more than one order of magnitude, the drive voltage at a fixed current increases, and the electron Schottky barrier height increases as the crystallinity of the film is increased. The diode current–voltage characteristic is determined by the dominant hole current and the electroluminescence efficiency is controlled by the contact limited electron injection. These results demonstrate significant effects of organic film structure on the performance of organic LEDs. ©1996 American Institute of Physics.