In this work, we present the possibility to electrochemically assist and study the interfacial polycondensation derived from the reactions between 1,6-diaminohexane or p-phenylenediamine (used as the diamine initially present in the aqueous phase) and acyl chlorides in a form of 1,3,5-benzenetricarbonyl trichloride, terephthaloyl chloride or adipoyl chloride (present in the organic phase – 1,2-dichloroethane solution). Polyamides are synthesized at the polarized liquid – liquid interfaces (or the interface between two immiscible electrolyte solutions – ITIES) as a consequence of the transfer of partly protonated diamines from the aqueous to the organic phase. In this respect, we have defined the aqueous phase pH assuring the availability of amine groups (-NH2) for the reaction with the acyl chloride and protonated amine groups (-NH3+) defining the electrochemical interfacial activity of chosen compounds. The possibility to electrochemically assist the interfacial formation of polyamides was first tested using the macroscopic ITIES. Formed polyamides were collected and analysed using scanning electron microscopy, energy dispersive x-ray spectroscopy and Raman spectroscopy. Next, we have employed the microscopic ITIES (microITIES) based system formed using fused silica microcapillaries. Cyclic voltammetry was employed for the polyamide modified microITIES assessment (evolution of molecular sieving properties using a model ion - tetramethylammonium cation)