In this work, a series of dendrimer functionalized ‘core-shell’ like oligo(phenyleneethynylene)s (OPEs) molecular wires have been reported. This new type of molecular wires could be well dissolved in common organic solvents, and form self-assembled monolayers (SAMs) on gold surfaces. Electrochemical investigation shows that the density of the SAMs depends on the size of the dendrimer ‘shell’. UV–vis absorption spectra and fluorescence emission spectra indicate that little aggregations occur in the solutions. Complication due to π–π interactions between OPEs decreases with the increase of the size of the dendrimer ‘shell’.