Two types of molecular and polymer devices employing (2-(4′-biphenyl)-5-(4″-tert-butylphenyl)-1,3,4-oxadiazole) (PBD) and poly(N-vinylcarbazole) (PVK) as electron transport and hole transport materials, respectively, have been fabricated. The structures of these two devices are ITO/PVK( 70 nm)/PBD (60 nm )/Al and ITO/PVK: PBD ( 1: 1 by mass, 70 nm )/Al. The formation of exciplex is evident by comparing the electroluminescence (EL) of a bi-layer device and the photoluminescence (PL) of a PVK and PBD mixed film.The maximum emission energy of exciplex evaluated is consistent with the peak emission of EL. Blue emissions from both devices are obtained. The type of exicplex is interpreted based on the energy level diagram of the bi-layer device.