A recently published method for quantifying refractory organic matter (often referred to as humic substances) in freshwaters was applied to a wide range of International Humic Substance Society (IHSS) humic compounds in order to (i) gain a better understanding of the mechanism of the voltammetric response which is the basis of the analytical method and (ii) provide guidance on choosing the optimal standard to be used. At the same time, the sensitivity of the technique has been increased by switching from the pulse mode initially proposed to the square-wave mode. The results obtained show that (i) differences in adsorption onto the electrode rather than differences in complexation strength are responsible for the differences in the intensity of the signal obtained for the different humic compounds, (ii) carboxylate, N- and S-containing groups do not play a role in the voltammetric signal.