The role of edge-plane-like defects at the open ends of multiwalled carbon nanotubes (MWCNTs) and at hole defects in the tube walls is explored using cyclic voltammetry with two charged redox probes, namely potassium ferrocyanide and hexaamineruthenium(III) chloride in unbuffered aqueous solutions, and one neutral redox probe, norepinephrine, in pH 5.7 buffer. Further, the presence of oxygen-containing functional groups (such as phenol, quinonyl and carboxyl groups), which decorate the edge-plane defect sites on the voltammetric response of the MWCNTs, is also explored. To this end, three different pre-treatments were performed on the pristine MWCNTs made using the arc-discharge method (arc-MWCNTs). These were (a) arc-MWCNTs were subjected to acid oxidation to form acid-MWCNTs—open-ended MWCNTs also possessing numerous hole defects revealing a large number of edge-plane-like sites heavily decorated with surface functional groups; (b) acid-MWCNTs, which were subsequently vacuum-annealed at 900 °C to remove the functional groups but leaving the many undecorated edge-plane-like sites exposed (ann-MWCNTs); (c) ann-MWCNTs, which were subjected to a further vacuum “super-annealing” stage at 1,750 °C (sup-MWCNTs), which caused the hole defects to close and also closed the tube ends, thereby, restoring the original, pristine, almost edge-plane defect-free MWCNTs structure. The results of the voltammetric characterisation of the acid-, ann- and sup-MWCNTs provide further evidence that edge-plane-like sites are the electroactive sites on MWCNTs. The presence of oxygen-containing surface groups is found to inhibit the rate of electron transfer at these sites under the conditions used herein. Finally, the two charged, “standard” redox probes used were found to undergo strong interactions with the oxygen-containing surface groups present. Thus, we advise caution when using these redox probes to attempt to voltammetrically characterise MWCNTs, and by extension, graphitic carbon surfaces.