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Biogenic amines (BAs) can be found in various foods, such as cheese, wine, and chocolate. The consumption of a sufficient quantity of BA can lead to symptoms including headaches, hypertonia, and diarrhea. For this reason, the amount of BA in food is regulated in many countries. A new method for the determination of biogenic amines in wine has been proposed, which involves derivatizing BA with p-toluene sulfonyl chloride (TsCl) and using K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> to reduce the matrix effect. The derivatives of putrescine, cadaverine, histamine, and tyramine with TsCl were synthesized and characterized by <sup>1</sup>H NMR spectroscopy. Separation of BA derivatives was performed using a reversed-phase high-performance liquid chromatography (RP-HPLC). The chromatographic system was equipped with a reversed-phase C8 column and a diode array detector. This method was validated to analyze the above-mentioned biogenic amines simultaneously in red and white wine samples. The detection limits for putrescine, cadaverine, histamine, and tyramine in wine samples were 0.0248 mg·L<sup>-1</sup>, 0.0645 mg·L<sup>-1</sup>, 0.346 mg·L<sup>-1</sup> and 0.00866 mg·L<sup>-1</sup>, respectively. The calibration curves showed good linearity (r > 0.999), and biogenic amines recovery varied from 83.0 to 110%. The proposed method demonstrates high sensitivity, straightforward sample preparation, and rapid analysis time.