Carbon nanotubes (CNTs) possess preferential 'electrocatalytic' properties that affect the oxidation of enediol groups, establishing a relationship between electrocatalysis and chemical structure. Since this chemical structure occurs in analytes involved in high impact areas such as the pharmaceutical, cosmetic, and food safety industries, this preferential electrochemical behaviour was demonstrated using both standard and selected real-world samples. The oxygen-containing species present on the surface of CNTs and generated during acid treatment were responsible for an enhanced electron transfer reaction for these structures using a proton-assisted electron transfer mechanism, thus confirming their crucial role during the surface preparation process of electrocatalysis. The analytical benefits were that the inherent selectivity and sensitivity from these nanomaterials could be exploited for the direct detection of analytes in complex matrices, revealing their crucial role in the simplification of analytical processes.