Exciplex bands in the electroluminescence (EL) spectra of electroluminescent devices based on the new zinc complexes of amino-substituted benzothiazoles and in the photoluminescence (PL) spectra of the blends of a zinc complex and the triphenylamine derivative are studied. For the EL spectra, it is found that the relation between the exciplex bands and the intrinsic bands of the zinc complex emission depends on the thickness of layers in the EL devices and on the applied voltage. For the PL spectra of blends, this relation strongly depends on the concentration of components.