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Thermally stimulated processes have been studied in thin films of phenanthroline derives to describe the states that had been localized. Ultraviolet Photoelectron Spectroscopy had checked out before thin films of new pyrrolo[l,2-a][l,10] phenanthroline derivatives [1], in order to further applications in optoelectronic devices. The investigated compounds have an electronic band structure which is due to the substituent (R=NO2, Cl) induced transformations of molecular orbitals. Thermally stimulated discharge currents (TSDC) attested dipolar and charge transport mechanisms. Each TSDC peak has been assigned to elementary processes that are different utilizing in addition dielectric spectroscopy (DES), and the mean trap depths have been approximated from thermally stimulated luminescence (TSL) curves.