The electro-oxidation of nicotinamide adenine dinucleotide (NADH) is studied at bare surfaces of highly oriented pyrolytic graphite (HOPG) and semi-metallic polycrystalline boron-doped diamond (pBDD). A comparison of these two carbon electrode materials is interesting because they possess broadly similar densities of electronic states that are much lower than most metal electrodes, but graphite has carbon sp2-hybridization, while in diamond the carbon is sp3-hybridised, with resulting major differences in bulk structure and surface termination. Using cyclic voltammetry (CV), it is shown that NADH oxidation is facile at HOPG surfaces but the reaction products tend to strongly adsorb, which causes rapid deactivation of the electrode activity. This is an important factor that needs to be taken into account when assessing HOPG and its intrinsic activity. It is also shown that NADH itself adsorbs at HOPG, a fact that has not been recognized previously, but has implications for understanding the mechanism of the electro-oxidation process. Although pBDD was found to be less susceptible to surface fouling, pBDD is not immune to deterioration of the electrode response, and the reaction showed more sluggish kinetics on this electrode. Scanning electrochemical cell microscopy (SECCM) highlights a significant voltammetric variation in electroactivity between different crystal surface facets that are presented to solution with a pBDD electrode. The electroactivity of different grains correlates with the local dopant level, as visualized by field emission-scanning electron microscopy. SECCM measurements further prove that the basal plane of HOPG has high activity towards NADH electro-oxidation. These new insights on NADH voltammetry are useful for the design of optimal carbon-based electrodes for NADH electroanalysis.