A new sample preparation method is proposed for the extraction of pharmaceutical compounds (Metformin, Phenyl biguanide, and Phenformin) of varied hydrophilicity, dissolved in an aqueous sample. When in contact with an organic phase, an interfacial potential is imposed by the presence of an ion, tetramethylammonium (TMA +), common to each phase. The interfacial potential difference drives the transfer of ionic analytes across the interface and allows to reach up to nearly 100 % extraction efficiency and a 60-fold enrichment factor in optimised extraction conditions as it is determined by HPLC analysis.