A multilayered electroluminescent device was constructed with ordered perylene thin films as an emission layer. The epitaxial perylene film was prepared by vapor deposition onto the KCl (001) surface, then removed from the KCl substrate and sandwiched between the hole-transport layer coated on an indium tin oxide electrode and Al top electrode. In this epitaxial layer, the perylene molecules oriented their molecular planes perpendicular to the electrode surfaces. This epitaxial device emitted an electroluminescence in the longer wavelengths of 560–580 nm due to the ordered dimeric structure. On the other hand, the device with polycrystalline perylene films exhibited an electroluminescence mainly below 500 nm.