The voltammetry of 2,3,5,6-tetramethyl-p-phenylenediamine, H2PD, has been studied and compared to that of its isomer N,N,N’N’-tetramethyl-p-phenylenediamine, Me2PD. Both undergo two reversible electron transfer processes in acetonitrile that nominally correspond to 1e- oxidation to the radical cations, Me2PD+ and H2PD+, and a second 1e- oxidation at more positive potentials to the quinonediimine dications, Me2PD2+ and H2PD2+. While the voltammetry of Me2PD agrees with this simple mechanism, that of H2PD does not. The second voltammetric wave is too small. UV/Vis spectroelectrochemical experiments indicate that the second wave does correspond to oxidation of H2PD+ to H2PD2+ in solution. The fact that the second wave is not present at all at the lowest concentrations (5 µM), and that it increases at longer times and higher concentrations, indicates that H2PD+ is not the initial solution product of the first oxidation. A number of lines of evidence suggest instead that the initial product is a mixed valent, H-bonded dimer between one H2PD in the the full reduced, fully protonated state, H4PD2+, and another in the fully oxidized, fully deprotonated state, PD. A mechanism is proposed in which this dimer is formed on the electrode surface through proton transfer and H-bonding. Once desorbed into solution, it breaks apart via reaction with other H2PD’s, to give 2 H2PD+, which is the thermodynamically favored species in solution.