An electrochemical investigation of 1,2- and 1,4-dihydroxybenzenes was carried out with platinum macro- and microelectrodes using square wave and cyclic voltammetry techniques. Furthermore, the effect of the two solvents—acetic acid and ethyl acetate—was compared. When using square wave voltammetry, signals only appeared at lower frequencies and only when the supporting electrolyte was in excess, as expected due to the relatively low permittivity of the used solvents. The behavior of hydroquinone and catechol did not differ significantly from that of their derivatives (dihydroxybenzaldehydes, dihydroxybenzoic acids and 2′,5′-dihydroxyacetophenone). When the cyclic voltammetric experiments using a microelectrode were extended to higher anodic potentials, electrode fouling was very significant in ethyl acetate after the potential region where steady-state oxidation to the corresponding quinone occurs. The substituent effect was not significant here either, which was proven by using different functional groups in different positions. In contrast, the position had a dramatic influence on the susceptibility to electropolymerization, as 1,2-dihydroxybenzenes—independent of the nature of the substituent on the benzene ring—deactivated the electrode, while 1,4-dihydroxybenzenes did not, possibly due to the different solubilities of the polymers formed from the primary oxidation product (quinones). A user-friendly analytical procedure is also proposed that uses an electropolymerization reaction and does not require frequent cleaning of the electrode via polishing, which is required usually especially with a microelectrode.