Electroplex emission based on poly(N-vinylcarbazole) (PVK) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) has been improved dramatically by using a multi-layer device structure indium-tin oxide (ITO)/poly(3,4-ethylenedioxythiophene): poly(styrenesulphonic acid) (PEDOT:PSS)/PVK/BCP/PVK/BCP/LiF/Al. Electroplex emission at 595nm has been improved about 10 times under low voltage and four times under high voltage compared to the double layer device ITO/PVK/ BCP/Al. The maximum brightness of the device also has been improved about eight times. Bright white emission via electroplex formation can be obtained with Commission International d’Eclairage (CIE) coordinates (0.336, 0.320) at 26V with a brightness of 123cd/m2. Based on the analysis of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the materials, we suggest the enhancement is mainly ascribed to the confinement effect of the quantum-well-like multi-layer device structure. Every hole and electron has more possibilities to cross recombination at the PVK/BCP interface.