Double adducts of norbornadiene-2,5 and anthracene derivatives have been synthesized using the Diels-Alder reaction. The possibility of selective preparation of both symmetrical and unsymmetrical adducts depending on the reaction conditions has been shown. For these cycloadducts exclusively consisting of carbon and hydrogen, an unusual and interesting feature has been revealed, namely, the signals of the protons of the bridge methylene groups in the H-1 NMR spectra have chemical shifts in the negative region. In this work, double adducts of anthracene derivatives and norbornadiene (2,5-(bicyclo-[2.2.1]-hepta-2,5-diene)) have been synthesized and their structure investigated. The synthesized compounds possess a rigid, branched, and bulky structure suitable for the fabrication of composite membrane materials.