The hydrogen bonding between phenolic compounds (phenol (Ph), catechol (Ct), resorcinol (Rs), and hydroquinone (Hq)) is investigated at pH 4. The oxidation behaviors of total phenolic compounds (TotPh) are different from their individual behaviors due to the existence of intermolecular hydrogen-bonded oligomeric clusters. Theoretical calculations and voltammetric and spectroscopic evidences support the intermolecular hydrogen bonding. The interaction of the phenolic compounds with polyaniline (PANI) and poly(vinylferrocenium) (PVF+) films are also investigated electrochemically and spectroscopically. The phenolic molecules are immobilized in both polymers due to the construction of hydrogen bonds by PANI and the complexation with PVF+. In addition, Ct and Hq are catalytically oxidized by PANI. Determinations of Ct and TotPh are performed on PVF+-PANI composite-coated Pt electrode using amperometric I-t method. Composite coating exhibits significant electrochemical activity toward Ct and TotPh, with high sensitivity and a wide linearity range. The steady-state currents versus concentration of Ct and TotPh are found to be linear in the range of 1.35 x 10(-3)-50.0 mM and 4.10 x 10(-4)-560 mM for two linear regions, respectively. (c) 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43596.