A newly developed in situ electron paramagnetic resonance (EPR)/ultraviolet-visible (UV-vis) spectroelectrochemical cell equipped with a laminated indium-tin oxide (ITO) working electrode was used in the investigation of various organic substrates which are potential hole-transporting materials. The experiment demonstrated the possibility of using such a technique for examining redox behavior of conducting polymers (polypyrrole, PPy), oligomers (thiophene dimmer and quarterthiophene) and bis-anilines (N,N,N',N'-tetraphenylbenzidine, TPB). All investigated structures formed stable paramagnetic intermediates in the first oxidation step characterised with UV-vis spectra in the region 400-600 nm. In the second oxidation step EPR-silent di-cationic structures are formed with broad vis bands in the region 600-1000 nm. The measurement of the reference UV-vis spectra direct in the EPR cavity was possible using a specially-constructed non-contacted ITO plate in the spectroelectrochemical cell in the case of polypyrrole.