The oxidation of substituted catechols was studied by cyclic voltammetry, chronoamperometry, rotating ring‐disk electrode, and coulometry. The results showed that the quinones that were formed from the oxidation of substituted catechols reacted with the basic forms of the starting material to yield the dimeric product. These products were generally unstable and rapidly polymerized or underwent some other irreversible reaction to form an electroinactive product. For 3,4‐dihydroxyacetophenone and propriophenone, the intermediate was stable long enough to be observed in cyclic voltammetry. The rate of the coupling reaction was found to correlate well with the Hammett ρ‐σ parameters and indicated that there was substantial negative charge in the transition state. Finally, an analysis of the coulometric n‐values along with the values indicated that the initial coupling product was a diphenyl ether. Analysis of the coulometry products showed extensive polymerization.