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This study involved an investigation into the electrochemical characteristic of a few biogenic amines (BAs) occurring at the polarized interface between two immiscible electrolyte solutions (ITIES) with ion transfer voltammetry (ITV). The main focus of this research was the comprehensive electroanalytical and physicochemical analysis of phenylethylamine (PEA), allowing the determined of the formal Galvani potential of the ion transfer reaction (Δ org aq Φ ' ), diffusion coefficients (D), formal free Gibbs energy of the ion transfer reaction (ΔG 'aq→org ) and water-1,2-dichloroethane partition coefficient (logP water/DCE PEA ). Furthermore, the collected data were employed to calculate analytical parameters, including voltametric detection sensitivity, limits of detection and the target analyte quantification. Moreover, the influence of the presence of 7 other BAs (histamine, spermine, spermidine, putrescine, cadaverine, tyramine and tryptamine) on the recorded signals originating from the PEA ion transfer was checked. The feasibility of the developed method was corroborated through experimentation with milk samples. Additionally, utilizing the devised methodology, an electrochemical assessment of the spoilage progression in milk samples was undertaken., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Konrad Rudnicki reports financial support was provided by National Science Centre Poland., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)