We report on the layer-by-layer assembly and electrochemical properties of 4-aminothiophenol (P-ATP) and ytterbium(III) trifluoromethanesulfonate hydrate (Yb(OTf)3) film supported on a gold surface. The fabricated film was characterised electrochemically using redox couples Fe(CN)63−/4−, complemented with imaging using atomic force microscopy (AFM). The electrocatalytic activity of the prepared electrodes was studied using cyclic and differential pulse voltammetries. Electrochemical measurements show that the P-ATP/Yb(OTf)3 modified electrode has superb activity towards hydroquinone (HQ) oxidation and that there is a significant improvement in the electrode stability and reproducibility due to the covalent and coordination reactions.