The formation and behavior of self-assembled monolayers made of n-dodecaneselenol (DDSe) on Au(111) as a blocking dielectric medium toward heterogeneous electron-transfer were assessed by electrochemical impedance spectroscopy. Microelectrode array theory was applied to study the growth kinetics of the self-assembled monolayer. The results show that adsorption from a n-dodecaneselenol solution in ethanol can be described using two different time constants. The monolayer is formed within the first minute after the electrode has been brought into contact with the deposition solution, The second step involves film reorganization and self-ordering, which can last for several hours.