Recently, the plant polyphenols have attracted much attention for membrane modification, especially in surface coating application. In this study, the synthesis of catechol-amine coating solutions was evaluated at different pH conditions and with different concentrations of tannic acid and tetraethylenepentamine in order to determine the relationship between chemical structure and mechanism in the oxidation reaction. The reactivity of catechol and amine groups in the formulation was measured using UV-Vis spectroscopy and observation of the change in colour of the coating solutions. Then, the deposition of catechol-amine coating solutions was applied onto the hydrophobic polyvinylidene fluoride (PVDF) membrane. The formulation results show significant differences in alkaline conditions, revealing the role of catechol groups in the oxidation of polyphenolics. The reactions of quinone and amines to form crosslinks by Michael addition and Schiff base reactions were observed at different concentrations of each compound in coating solution. In addition, the negative charge of hydrophilic and underwater oleophobic-coated PVDF membrane was confirmed by surface zeta potential analysis. The morphological surface of modified membrane is rougher due to that coating deposition was also examined using scanning electron microscopy (SEM). Furthermore, the performance of modified membrane is comparable with the commercial hydrophilic membrane in terms of fluxes and separation efficiency of emulsion solution.