This report seeks to address the role of hydrogen bonding with Bronsted acids and bases in proton-coupled electron transfer (PCET) as it pertains to concerted or stepwise pathways of quinone (Q) and hydroquinone (QH(2)) electrochemistry. This study was performed using a series of techniques that included cyclic voltammetry (CV), digital simulations, computational chemistry and H-1 NMR. Hydrogen bonding was inferred by a decrease in diffusion coefficient (D) values measured using a pulsed gradient echo- (PGE-) H-1 NMR technique. Changes of 40.8% and 37.9% in D values were only noted after the addition of two equivalents of acetate to 1,4-hydroquinone (1,4-QH(2)) and catechol (1,2-QH(2)), respectively. In contrast, the D values for the addition of selected amines (pyridine, N,N-diisopropylethylamine and triethylamine) changed only 3.2% on average. Quantum mechanical calculations were conducted to determine the pK(a) of all quinoid species to serve as a starting point for the determination of equilibrium constants in voltammetric simulations. Simulations indicate that 1,4-benzoquinone undergoes stepwise electron-proton transfer upon addition of acetic acid, N-ethyldiisopropylammonium perchlorate and pyridinium nitrate and were simulated without the presence of hydrogen bonds. The QH(2) compounds show stepwise proton-electron transfers after addition of the both the conjugate amines and acetate. Published by Elsevier Ltd.