The considerable need for novel polyaromatic hydrocarbons (PAHs) for applications in the area of organic electronics remains unchanged. Diacenaphthopyrene represents a new PAH consisting of two acenaphthylene units connected by a pyrene bridge. The system is built up by Pd-catalyzed cross-coupling, followed by acid catalyzed cyclosiomerization to generate the pyrene moiety. The new fused scaffold is formed in the last step in convincing yields by means of CH-activation. We additionally synthesized one aza-pyrene based analogue. The two hitherto unknown PAHs were investigated in detail by UV-Vis and PL spectroscopy, CV measurements and DFT calculations. Based on these results, the abilities of the novel structure as well as the effect of incorporation of nitrogen were evaluated.