Chemically modified electrodes based on complexes of transition metals with N,N′-ethylenebis(salicylimine) (salen) type ligands are reported to act as redox mediators due to axial coordination of exogeneous ligands to metal atom in oxidized form of complex. Thus such electrodes can be used as amperometric and voltammetric detectors of various compounds. However, effects of ligand structure and ligand-analyte specific interactions on the electrochemical response of said complexes have not been studied yet for organic analytes. In this article we demonstrate that some aromatic amines can interact with salen-type ligands by several routes, depending on the ligand and amine structure. It leads to the ligand polarization, and thus to the unique shape of voltammetric curves of chemically modified electrodes, based on polymeric salen complexes, immersed in amines solutions. Such feature allows using the electrodes as sensors for molecular recognition. The same electrodes can act as electron transfer catalysts of the amines oxidation, and may be applicable to the quantitative analysis of amines with the detection limit about 10 μmol l⁻¹.