Results of theoretical and experimental studies of exciplex of a zinc complex Zn(DFP-SAMQ)2 with the hole-transporting layer of NPD are presented. It is shown that at least three different arrangements of Zn(DFP-SAMQ)2 and NPD molecules in the excited state result in the long-wavelength charge-transfer emission bands. At the same time, such systems are unstable in the ground state.