We report light emission from light emitting diodes with poly(3‐octylthiophene) (P3OT) as the active layer in both forward and reverse bias operation. The onset of electroluminescence (EL) of ITO/P3OT/Al devices occurs at current densities of 6.25×10−4 A/cm2 in both modes of operation; both cases show identical EL spectra. For a P3OT thickness of 100 nm the onset of electroluminescence and current occurs at 3 V in the forward bias mode, and at about 18 V in the reverse mode of operation, at which a completely different voltage dependence of the current is observed. In the reverse mode of operation, the data suggest that carrier injection is a tunneling process through a triangular barrier of 0.4 eV at the metal–polymer interface. In the forward bias a Schottky‐like behavior is seen.