The adsorption of aromatic molecules at solid/liquid interface represents one important topic in surface science because of its close relationship with the surface catalysis, molecular-based nanostructure and nanodevices, and other surface physical chemistry phenomena. With the high-resolution images of molecular adlayer obtained by electrochemical scanning tunneling microscopy (STM), the abundant information about the adsorption structure and dynamics of aromatic molecules on electrode surfaces was obtained. The results are important to the understanding of the intermolecular and molecular-substrate interactions which govern the formation of adlayers. In the present review, the development of electrochemical STM was briefly reviewed and the progress of the study on the adsorption of aromatic compounds and their derivations on electrode surface was introduced. In particular, the attention is paid on the adsorption of hetero-cyclic aromatic compounds and other derivatives to elucidate the interaction of different functional groups with the substrate and the effect of molecule symmetry, electronic structure on the adsorption process.