The synthesis of covalently linked dimers, containing two resorcin[4]arene moieties connected over two 9,10-functionalized anthracene units, is reported. Besides the synthetic route, which involves for example the formation of anthracene-9,10-dialkanols ( and ), and characterization of the compounds, the photochemical properties, introduced through the anthracene groups, were investigated by means of UV/VIS spectroscopy. Both resorcin[4]arene dimers ( and ) were able to undergo an intramolecular [4+4] cycloaddition, therefore changing the size of the inner cavity. Unfortunately, the back reaction, which was expected to take place on irradiation below 300 nm or upon heating, was not observed yet and will be the focus of our future work.