The effect of components of the redox pair K3[Fe(CN)6]/K4[Fe(CN)6] on the dynamics of formation of octanethiol (OT) monolayers from aqueous thiol-containing solutions of 0.1 М NaClO4 is studied by cyclic voltammetry (CVA). The formation of OT monolayers is shown to depend on the presence of ions of hexacyanoferrate(II)/(III) in solution. Being added to solution, the components of the [Fe(CN)6]3–/4– redox pair sharply increase the time of formation of the insulating monolayer OT films and make them less stable. The destabilizing and inhibiting action of [Fe(CN)6]3–/4– ions becomes stronger as their concentration in solution increases. The adsorption activity of individual components of the redox pair is assessed. The strong and approximately equal adsorption activity of ions [Fe(CN)6]3– and [Fe(CN)6]4– on gold in the presence of octanethiol is observed. At the same time, OT and the hexacyanoferrate(II)/(III) ions can be placed in the following row: OT > [Fe(CN)6]3– ≈ [Fe(CN)6]4–. Recommendations are given on how to eliminate the interfering action of the K3[Fe(CN)6]/K4[Fe(CN)6] redox-pair ions when studying the insulating properties of thiol monolayers on gold.