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)(6)(3-/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.