The PL and EL spectra of poly(N-vinylcarbazole) (PVK): 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) (1:1w/w) film were found completely different. The PL spectrum is a single peak at 415 nm that originates from excitons emission from PVK, and the tail of the spectrum is suggested to be excimer emission from BCP molecules. However, a new emission at 595 nm was found in the EL spectra of devices ITO/PEDOT:PSS(50nm)/PVK:BCP (1:1)(100nm)/Al. After aggregate, exciplex and product of electrochemical reaction were ruled out, the new emission was proposed to be electroplex emission that occurred between PVK and BCP molecules. Under high voltage, only electroplex emission can be observed in the EL spectra.