Oriented sexiphenyl (6P) film was prepared through epitaxial growth on rubbed substrates by vacuum deposition. Polarized absorption spectra demonstrated that the long axis of 6P molecule was highly oriented along the rubbing direction. Using the epitaxial growth film of 6P, we fabricated electroluminescent (EL) devices consisting of indium‐tin‐oxide anode, emissive layer of 6P, electron‐transporting layer of an oxadiazole derivative, and MgAg alloy cathode. Owing to the orientation of 6P molecules, EL polarized in the rubbing direction was observed in the devices.