Utility of self assembled monolayers would be extended if they could be easily functionalized with chemical moieties of interest. Forming SAMs from such tethered moieties does not guarantee that they will form a well ordered SAM. To circumvent this potential problem, we have studied and developed conditions for well ordered binary SAMs of azidoalkanethiol and alkanethiol and react the azido functional SAMs using “click” coupling chemistry with alkyne functional moieties. We have been able to demonstrate molecularly-resolved STM imaging of these mixed monolayers before and after the reaction.