Electrochemical studies on gold electrodes covered with self-assembled monolayers (SAM) of aminoethane thiol (AET), mercaptobenzothiazole (MBT) and octadecyl mercaptan (ODM) have been carried out using cyclic voltammetry. Study of the influence of these monolayers on the double layer capacity of the interfaces involving the Au/SAM electrodes and of the electron transfer kinetics of chosen redox reaction probes, viz., Fe(CN)₆^4−/3−, Fe^2+/3+, hydroquinone/quinone(H₂ Q/Q) and Cu underpotential deposition, offers a wealth of information that can throw light on the role of SAMs in allowing/moderating/blocking the electron transfer at such interfaces. These details are presented and discussed in the paper.