The luminescence spectra of carbazole and phenyl-substituted amines in. toluene solution. and wide set of polymer matrix were studied at 5 and 295 K, as well as their parameters were obtained. The intersystem crossing was shown to be important process influeucing on the energy relaxation. of excited singlet state. Its efficiency depends not only on. the chemical nature of substituents and spatial conformation. of molecule, but also is conditioned by interaction. with ambient medium. Therefore, the rate of intersystem conversion increases upon influence of external heavy atom, and also when. the polymer matrix is changed or pressure up to 3 kbar is applied.