Organic electroluminescent (EL) single-layer (SL) and double-layer (DL) light-emitting diodes were fabricated based on 4,4′,4″-tris[3-methylphenyl(phenyl)amino] triphenylamine (m-MTDATA) and 2-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) molecules incorporated in bisphenol-A-polycarbonate (PC) matrix. The external EL quantum efficiency of the dominating exciplex emission of the indium tin oxide (ITO)/m-MTDATA:PBD:PC/Ca SL structure is ≅0.4% photon/electron and that from the ITO/m-MTDATA:PC/PBD/Ca DL device exceeds 1% photon/electron. The operating voltage of the DL device at maximum efficiency is 4.8 V and the onset voltage of the EL is as low as 2.0 V. The photoluminesce quantum efficiency of the exciplex is greater than 17%. The high exciplex emission-based EL yield from the DL device is attributed to the narrow recombination zone imposed by the high energy barriers for the electron and hole transfer at the (m-MTDATA:PC)/PBD interface.