The electro-oxidation of dopamine (DA) is investigated on the unmodified surfaces of five different classes of carbon electrodes: glassy carbon (GC), oxygen-terminated polycrystalline boron-doped diamond (pBDD), edge plane pyrolytic graphite (EPPG), basal plane pyrolytic graphite (BPPG), and the basal surface of highly oriented pyrolytic graphite (HOPG), encompassing five distinct grades with step edge density and coverage varying by more than 2 orders of magnitude. Surfaces were prepared carefully and characterized by a range of techniques, including atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and Raman spectroscopy. Although pBDD was found to be the least susceptible to surface fouling (even at relatively high DA concentrations), the reaction showed sluggish kinetics on this electrode. In contrast, DA electro-oxidation at pristine basal plane HOPG at concentrations ≤100 μM in 0.15 M PBS, pH 7.2, showed fast kinetics and only minor susceptibility toward surface fouling from DA byproducts, although the extent of HOPG surface contamination by oxidation products increased substantially at higher concentrations (with the response similar on all grades, irrespective of step edge coverage). EPPG also showed a fast response, with little indication of passivation with repeated voltammetric cycling but a relatively high background signal due to the high capacitance of this graphite surface termination. Of all five carbon electrode types, freshly cleaved basal plane HOPG showed the clearest signal (distinct from the background) at low concentrations of DA (<10 μM) as a consequence of the low capacitance. Studies of the electrochemical oxidation of DA in the presence of the common interferents ascorbic acid (AA) and serotonin (5-HT), of relevance to neurochemical analysis, showed that the signals for DA were still clearly and easily resolved at basal plane HOPG surfaces. In the presence of AA, repetitive voltammetry caused products of AA electro-oxidation to adsorb onto the HOPG surface, forming a permselective film that allowed the electrochemical oxidation of DA to proceed unimpeded, while greatly inhibiting the electrochemical response of AA itself. The studies presented provide conclusive evidence that the pristine surface of basal plane HOPG is highly active for the detection of DA, irrespective of the step edge density and method of cleavage, and adds to a growing body of evidence that the basal plane of HOPG is a much more active electrode for many classes of electrode reactions than previously believed.