The discovery and investigation of exciplex luminescence in the polyatomic molecule vapors1-4is of great importance for better understanding of the relaxation mechanisms in bimolecular complexes formed due to the charge transfer between photo-excited organic molecules and other type of molecules in the ground state. The study of the vapor-phase exciplex emission from 9, 10-dicyanoanthracene in the presence of N, N-dimethylaniline (9, 10-DCA + DMA) showed4that the exciplex stabilities, their luminescence properties and the relative efficiency of monomer and exciplex luminescence essentially depend on the excess of the vibrational energy of excited 9, 10-DCA molecules.