Polycyclic π-conjugated hydrocarbons (PCHs) have attracted wide attention from the scientific community due to their prominent role as organic semiconductors and electroactive materials for the development of organic electronics. Linearly fused rigid systems, such as acenes, are considered paradigmatic organic semiconductors, 2 but their general use is hampered by the decreased chemical stability associated to the extension of the length of the acene, a feature that can be qualitatively explained on the basis of Clar's πsextet rule. Angularly fused phenes, starphenes and other bent-shaped oligoacene derivatives are also promising optoelectronic materials. Among the diverse families of PCHs, those containing fused fourmembered cyclobutadienoid rings are particularly interesting due to the properties associated with the alternation of aromatic and antiaromatic ring currents in their structures. In this context, in addition to the fascinating linear, angular and helical [N]phenylenes, profusely studied by Vollhardt and co-workers 7 among others, recent interest has aroused on the study of other polycyclic systems, including linear phenylenecontaining oligoacenes and heteroacenes, 10 derivatives with non-linear polycyclic aromatic moieties or isomeric graphene nanostructures formed by fused biphenylene units. 12 Biphenylene-containing PCHs have been recently explored for single-molecule junctions, or as potential singlet fission chromophores, while the effect of the cyclobutadiene rings on Baird aromaticity and its influence in the triplet state energies of the resulting π-extended derivatives have also been studied. Conversion of PCHs containing cyclobutadiene (CBD) rings into contorted benzenoid conjugated hydrocarbons, through metal-catalyzed C-C bond activation, has also been recently described. Some years ago, we applied our shortly before discovered palladium-catalyzed [2+2+2] cycloaddition of arynes 17 to the synthesis of tris-(benzocyclobutadiene)triphenylene. More recently, we used this biphenylene trimer as a probe for the siteselective covalent functionalization of a semiconductor surface. Our renewed interest in PCHs containing four-membered rings, led us to plan the synthesis of π-extended derivatives, including CBDcontaining oligoacenes, by means of cycloaddition reactions of a benzobiphenylene-based aryne building block, 2,3-didehydrobenzo [b]biphenylene (1), accessed from its Kobayashi-type aryne precursor 20 2 (Scheme 1). Here we report the results of our synthetic study, and the preliminary evaluation of the electronic properties and aromatic character of the newly synthesized CBD-containing PCHs.