In the years to come more and more processes at solid/liquid interfaces will replace processes which nowadays are carried out by vacuum based methods, like surface modification, thin film growth, nanostructuring, etc.. Among others this is a consequence of the growing number of methods which are capable to provide in-situ information about properties and processes at solid/liquid interfaces with the same precision as we are used to in vacuum. This is particularly true for ElectroChemical Scanning Tunneling Microscopy (ECSTM), which - in combination with in-situ FTIR- and some ex-situ spectroscopies - is used in this work to characterize copper single crystal electrodes interacting with various electrolytes. Firstly, surface structural phase transitions and morphological changes due to the adsorption of simple anions, like Cl, Br, J, S, SO@sub 4@, SCN, etc., will be studied with atomic resolution. Secondly, it will be shown that the halogen and sulphur covered electrode surfaces are interesting primary templates for the formation of thin ordered compound films (e.g. CdCl@sub 2@)) as well as self-assembled organic nanostructures (e.g. from porphyrins and viologenes). In particular the latter ones are found to form chiral cavitands, which in turn are ideal secondary templates for the design of more complex molecular architectures with nanoscale periodicity and specific functionality.