The two naphthol isomers were investigated in different organic solvents by taking cyclic voltammograms, and fouling took place on a platinum electrode surface, except for dimethyl sulfoxide and dimethyl formamide. Studies in allyl alcohol rarely used in electrochemical investigations pointed to the importance of the carbon–carbon double bond as electrode deactivation was remarkably faster compared with its saturated analog solvent. Similarly, the use of the other unsaturated solvent mesityl oxide in the electropolymerization of naphthols resulted in different findings compared with methyl isobutyl ketone. As dimethyl formamide was the best choice concerning the solubility of products, it was successfully tested in electrode renewal after deactivation in an aqueous solution. The increase in dimethyl formamide content led to more and more improved reproducibility of the currents of the outlined aromatic compounds. Naphthol isomers were assessed in the suppression of layer growth originating from the electrooxidation of another monomer phloroglucinol. Its simultaneous electrooxidation with naphthol monomers had a dramatic effect on layer morphology and it was found that instead of a coherent organic layer originating from the homopolymerization of phloroglucinol, the copolymerization with naphthols led to the development of more porous and rougher deposits. The suppressed electropolymerization thus increased sensitivity towards a chosen redox active compound, 4-methoxyphenol.