This work describes the syntheses, crystal structures, photophysical properties, and electro-chemical analyses of benzo[k]fluoranthene-based linear acenes, together with ab initio density functional theory computations on them. The molecules were prepared in generally moderate to good yields through Pd-catalyzed cycloadditions between 1,8-diethynylnaphthalene derivatives and aryl iodides. This protocol is simpler and more efficient than conventional methods. The scope and limitations of this reaction were examined. The structures of compounds 4hb, 15ac, 17ab, 19ac, and 24je were determined by X-ray analysis; they are either bent or twisted, rather than planar. The photophysical and electrochemical properties of these cycloadducts were also investigated and compared with computational predictions based on density functional theory.